Polymerization modifiers

ABSTRACT

A composition comprising a polymerization modifier for the copolymerization of at least one olefin monomer and propylene and a polymerization process using the polymerization modifier.

CROSS REFERENCE STATEMENT

The present application is a divisional application of the U.S.application Ser. No. 12/434,436, filed on May 1, 2009, now U.S Pat. No.7,943,546, entitled “POLYMERIZATION MODIFIERS,” which is a divisional ofthe U.S. application Ser. No. 11/596,336, filed on Nov. 9, 2006, now U.SPat. No. 7,553,917, entitled, “TECHNIQUE FOR SELECTING POLYMERIZATIONMODIFIERS CROSS REFERENCE STATEMENT,” which is a national phase of theInternational Application No. PCT/US05/16792, filed on May 13, 2005,entitled, “TECHNIQUE FOR SELECTING POLYMERIZATION MODIFIERS,” theteachings of which are incorporated by reference herein, as ifreproduced in full hereinbelow, and which claims priority from the U.S.Provisional Application No. 60/580,330 filed on Jun. 16, 2004, entitled“TECHNIQUE FOR SELECTING POLYMERIZATION MODIFIERS,” the teachings ofwhich are incorporated by reference herein, as if reproduced in fullhereinbelow.

BACKGROUND

The present invention relates to the field of research for new catalystcompositions especially for use in polymerization processes. Moreparticularly, this invention is directed toward an apparatus and methodof performing homogeneous, and supported homogeneous catalysis employingcompositions comprising a transition metal complex, a cocatalyst, andone or more polymerization modifier(s); as well as related techniquesfor rapidly creating and testing libraries of such compositions. Thisinvention is also directed toward the use of certain catalystcompositions having improved properties in olefin polymerizations.

Combinatorial and other high through-put techniques have been used torapidly screen large numbers of compounds for use in biological, organicand inorganic synthesis and research. Combinatorial materials sciencegenerally refers to the methods for creating a collection of chemicallydiverse compounds or materials and to methods for rapidly testing orscreening this library of compounds or materials for desirableperformance characteristics and properties. Areas for application ofsuch combinatorial methods have included the discovery of inorganiccompounds for use as high-temperature superconductors, magnetoresistivematerials, luminescent compounds, and catalysts. Examples include U.S.Pat. Nos. 5,712,171, 5,776,359, 5,985,356, 6,004,617, 6,030,917,6,045,671, 6,248,540, 6,326,090, 6,346,290, and 6,627,571, EP-A-978,499,and WO 00/40331.

In addition to the foregoing patent references, numerous academic papershave also disclosed combinatorial techniques, including: Senkan, Nature,vol. 394, pp. 350-353 (Jul. 23, 1998); Burgess et al., Angew. Chem. Int.Ed. Eng., 1996, 35, No. 2, pp. 220-222; Maier et al., Angew. Chem. Int.Ed. Eng., 1998, 37, No. 19, pp. 2644-2647; Reetz et al., Angew. Chem.Int. Ed. Eng., 1998, 37, No. 19, pp. 2647-2650; Angew. Chem. Int. Ed.Eng., 1998, 37, No. 17, pp. 2333-2336; Morken et al., Science, vol. 280,pp. 267-270 (Apr. 10, 1998); Gilbertson et al., Tetrahedron Letters,vol. 37, no. 36, pp. 6475-6478 (1996), and Boussie, et al., JACS, 2003,125, 4306-4317.

In WO 00/40331 a combinatorial apparatus and method for evaluatinghomogeneous and supported homogeneous coordination polymerizationcatalysts including olefin polymerization catalysts employing a metalcompound formed from a metal of Groups 3-15 of the Periodic Table of theElements and one or more ligands is disclosed.

Although the foregoing and other references have advanced the art ofcombinatorial materials testing, still further improvements and advancesare desired. In particular, more rapid techniques of screening candidatematerials are desired. Moreover, while combinatorial techniques havebeen applied to the discovery of simple metal complex/cocatalystcombinations, more complex compositions including a polymerizationmodifier have not previously been treated to combinatorial techniques.More specifically, there remains a need to apply combinatorialtechniques to rapidly screen and evaluate catalyst compositionscomprising a polymerization modifier. Accordingly, there remains a needfor a combinatorial method and apparatus for the rapid and reliablediscovery and development of polymerization modifier containingcompositions that is particularly adapted to use in olefinpolymerizations.

Various transition metal complexes and catalyst compositions containingthe same are previously known in the art. These complexes and methodsfor their preparation are described, inter alia, in U.S. Pat. Nos.5,703,187, 6,013,819, 5,189,192, 5,532,394, 5,470,993, 5,486,632,5,770,538, 5,495,036, 6,015,868, 6,153,776, 6,107,421, 5,866,704,6,268,444, 6,034,022, 6,150,297, 6,515,155, 6,613,921, 5,972,822,5,854,362, 5,892,076, 5,817,849, 6,084,115, 6,103,657, and 6,284,905 inpublications 2003US 0204017, 2002US 0142912, WO 2000 020377, WO2000/40331, and WO 2002 038628, and elsewhere.

Various cocatalysts, activators and activating techniques are similarlyknown in the art for use in combination with the foregoing metalcomplexes. Examples of references wherein cocatalysts are disclosedinclude the foregoing list of patents and publications as well as U.S.Pat. Nos. 5,064,802, 5,321,106, 5,721,185, 5,372,682, 5,783,512,5,919,983, 6,344,529, 6,395,671, 6,214,760, and elsewhere.

Known compounds that have been previously disclosed for use incombination with transition metal complexes and cocatalysts in olefinpolymerizations include alumoxanes, aluminum alkyls, and metal alkoxy oramide compounds, as disclosed in U.S. Pat. Nos. 5,453,410, 5,721,183,6,074,977, 6,017,842, 6,214,760, 6,387,838, and elsewhere.

SUMMARY OF THE INVENTION

This invention provides methods and apparatus for performing thecombinatorial synthesis of libraries and screening of thosecombinatorial libraries particularly adapted for use in homogeneous orsupported homogeneous addition polymerizations employing catalystcompositions comprising a polymerization modifier.

The broadest concept of the methodology is that a library of catalystcompositions is created and screened for olefin polymerization activity,especially by measurement of process variables under polymerizationconditions or properties of the resulting polymer product. The librariesthat are created are typically formed from arrays of organometalliccompounds or mixtures or multi-level arrays thereof by one or moreconversion steps to form catalyst compositions. The catalystcompositions comprise at a minimum a transition metal compound orcomplex, a cocatalyst able to convert the catalyst into an active olefinpolymerization composition, and a polymerization modifier. The resultingproducts are screened for polymerization activity under additionpolymerization conditions and/or properties of the resulting polymer.This invention provides a number of embodiments for performing suchsynthesis and screening, and the embodiments may be combined together.

In the library, each member may have a common property or functionality,but will vary in structural diversity, molecular weight or some othervariable to be tested (rational variation). Alternatively, the librarymay contain a mixture of diverse compounds with no unifying feature orstructure (random variation). The individual members of the librarydiffer from each other in some chemically significant manner, however,for purposes of calibration and statistical analysis, some repetition oflibrary members may be desired. Optionally, one or more daughterlibraries may be created from the parent library by taking one or morealiquots from one or more members of the parent library and combiningthem, optionally with any additional components. For example, eachdaughter library may be considered to be a replica of the originallibrary, but include one or more additional components or chemicaloperations. At least one transition metal complex should be present inat least a portion of the members of the precursor library or a daughterlibrary to create one or more catalyst libraries, which are thensubjected to addition polymerization conditions. The polymerization maybe used to create a product library, that is, a polymer library.Alternatively, the polymerization may serve as a screen for activity.The process conditions may also be combinatorialized, such as by varyingamounts of reactants or different polymerization conditions such astime, temperature, pressure, stirring rate, order of reagent addition,impurity type and amount, and so forth. The method optionally mayprovide different screening stages, such as a primary screen toeliminate some members from a library from going on to a secondaryscreen. One or more members of the library or the precursors thereto maybe substituted with a known standard, a blank, or an inert compound tofurther identify desired properties.

One embodiment of the present invention particularly adapted forresearching for novel catalyst compositions according to the inventionstarts with a transition metal complex library that includes a pluralityof member compounds, comprising at least one transition metal complex orprecursor thereto. The complexes generally will differ by composition,by structure, or by both composition and structure. Examples includecomplexes such as hydrocarbyl, chloride or amide derivatives of a metalsof Groups 3-11 of the Periodic Table of the Elements, containing atleast one π-bonded ligand group or at least one electron donative ligandgroup, as well as Lewis base containing derivatives of such compounds,or mixtures of the foregoing compounds. If desired, the library may alsobegin with precursors to the foregoing transition metal complexes and/orligands thereof and incorporate an additional level of synthesis inpreparing a daughter library comprising the desired transition metalcomplexes.

The library (transition metal complex library, cocatalyst library orpolymerization modifier library) may be subjected to one or moreconversion processes that may involve one or more steps or repetitionsof steps involving one or more reagents or treatments in order to form acatalyst composition to be screened. Examples of such conversionprocesses include metallation, metathesis or other chemical conversionof the transition metal complex or precursor, addition of one or moresolvents, mixing, heating, cooling, filtering, extracting, or simplyaging, and finally combination with a cocatalyst and one or morepolymerization modifiers. Separate libraries of such cocatalysts andpolymerization modifiers or the components used to prepare the same, mayalso be employed in combination with the library of transition metalcomplexes (or precursors thereof) in order to evaluate and screenvarious combinations of transition metal complex, cocatalyst andpolymerization modifier, and processes for forming such cocatalyst orpolymerization modifier.

The foregoing manipulations require the use of a cell or other suitablereaction vessel capable of allowing measured addition of reagents,adequate mixing and manipulation of the resulting reaction mixtures,heating and or cooling of the reactor contents, separations of products,and removal of by-products, solvents, or other constituents. Desirably,each reaction cell or vessel is sealed and subjected to an inertatmosphere or otherwise isolated from the atmosphere, other reactioncells, and from the library or libraries in order to prevent loss ofvolatile reactor components or contamination of other reagents,reactors, or reactions. In one embodiment, each reactor or cell isequipped with or has access to a filtration means that allows for readyseparation of liquids from solid reactor contents in the cell. Thefiltration device may be externally mounted and inserted into the cellfor purposes of performing the foregoing separation and thereafterremoved or disengaged from the cell upon completion of the separation.Alternatively, each cell may include a filter medium, such as a frittedglass surface in contact with the reactor contents and a valve or otherselector means, for separation/removal of liquid components. If desired,the apparatus may additionally include separate reaction vessels forpretreatment or formation of the various components, especially thepolymerization modifier, prior to charging to the reaction cell.

In another embodiment, mixtures of starting components (such as ligands,organometal compounds, metallated derivatives, cocatalysts,polymerization modifiers, additives, monomers, solvents, impurities, andso forth) are combined in different ratios, orders, or methods. Thepolymerization is performed under varying conditions to create a productlibrary or array. In this embodiment the conditions of thepolymerization process may be variables that are combinatorialized.Suitable process conditions that may be combinatorialized includeamounts and ratios of starting components, repetitions of process steps,purification and recovery of metal complex, polymerization modifier, orcatalyst compositions, order of addition of catalyst compositioncomponents, time allowed for formation of catalyst composition or anycomponent thereof, catalyst formation reaction temperature and pressure,rate of starting component addition to the reaction, residence time (orproduct removal rate), polymerization temperature, pressure, reactionatmosphere, mixing rate, and any other conditions that those of skill inthe art will recognize.

In addition, the foregoing embodiments can be combined together. Forexample, this invention may be practiced by having diversity in thestarting components used; by having diversity in the reaction conditionsused to form the catalyst library (such as time, temperature, mixingspeed, or other conditions used in catalyst formation); by diversity inthe polymerization conditions used; or by a combination of all theforegoing variables. The library of polymer products is screened bymeasurement of polymerization conditions such as heat generated, or morepreferably, consumption of one or more monomers, or by resulting polymerproperties, such as molecular weight or molecular weight distribution.The polymer library may also be tested to determine if a polymer ofinterest has been created using conventional analysis techniques or byuse of one of many different rapid polymer characterization techniques.

Because polymer properties can be adversely affected by post reactorconditions, physical testing of product properties may not be anaccurate indicator for screening of candidate materials. Polymerproperties are often preserved after formation until physical testingcan be conducted through the addition of antioxidants, stabilizers andother preservatives to the polymer sample. Incorporating and adaptingthe use of such additives to the small sample size typically employed incombinatorial materials testing can be highly impractical and addsignificantly complexity, delay and cost to the resulting protocol.Moreover, adequate and reproducible incorporation throughout the librarycan prove difficult and at a minimum introduces another source ofvariability. Accordingly, a preferred screening method for use in thepresent invention is the testing and recording of process conditionsencountered during polymerization.

The embodiments of this methodology may be combined into a flexiblesystem that includes a number of different stations including one ormore stations for combining starting materials, daughtering thelibraries, performing the reactions of interest, and screening theresults of the process. The system includes a control system thatcontrols, monitors and directs the activities of the system so that auser may design an entire series of experiments by inputting librarydesign, screening, and/or data manipulation criteria.

Those of skill in the art will appreciate the variety of methods forcreating diversity in the libraries of this invention. The screens areemployed to determine if the diversity has produced a product or processof interest, preferably by directly measuring one or more processparameters, thereby providing a quantifying means for evaluating theindividual members of the library. Through careful application of theprinciples outlined herein, the present inventors have now succeeded inproviding a combinatorial research technique that is specificallyadapted for the identification of catalyst compositions comprising atransition metal complex, a cocatalyst and a polymerization modifier.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1-5 are the chemical structures of the metal complexes (catalystprecursors) identified as C1, C2, C3, C4 and C5 in Examples 1-4.

DETAILED DESCRIPTION

All reference to the Periodic Table of the Elements herein shall referto the Periodic Table of the Elements, published and copyrighted by CRCPress, Inc., 2001. Also, any reference to a Group or Groups shall be tothe Group or Groups as reflected in this Periodic Table of the Elementsusing the IUPAC system for numbering groups. For purposes of UnitedStates patent practice, the contents of any patent, patent application,or publication referenced herein are hereby incorporated by reference intheir entirety (or the equivalent US version thereof is so incorporatedby reference) especially with respect to the disclosure of synthetictechniques, raw materials, and general knowledge in the art. Unlessstated to the contrary, implicit from the context, or customary in theart, all parts and percents are based on weight.

If appearing herein, the term “comprising” and derivatives thereof isnot intended to exclude the presence of any additional component, stepor procedure, whether or not the same is disclosed herein. In order toavoid any doubt, all compositions claimed herein through use of the term“comprising” may include any additional additive, adjuvant, or compound,unless stated to the contrary. In contrast, the term, “consistingessentially of” if appearing herein, excludes from the scope of anysucceeding recitation any other component, step or procedure, exceptingthose that are not essential to operability. The term “consisting of”,if used, excludes any component, step or procedure not specificallydelineated or listed. The term “or”, unless stated otherwise, refers tothe listed members individually as well as in any combination.

Highly desirably, the methodology of the present invention involvesselection of the desired catalyst composition based on optimization ormaximizing at least two and, more preferably, at least 3 process orproduct variables, measured pursuant to the present screening procedure.

Catalysts

Transition metal compounds for use herein include compounds or complexesof metals selected from Groups 3-11, preferably Groups 4-8 of thePeriodic Table of the Elements, most preferably Group 4, that is,titanium, zirconium and hafnium. Preferred compounds are thosecontaining one or more delocalized, π-bonded ligands or polyvalent Lewisbase ligands. Examples include metallocene, half-metallocene,constrained geometry, and polyvalent pyridylamine base complexes. Thecompounds are generically depicted by the formula: MK_(k)X_(x)Z_(z), ora dimer thereof, wherein

M is a transition metal selected from Groups 3-10 of the Periodic Tableof the Elements, preferably of a metal of Groups 4-8, most preferably aGroup 4 metal;

K independently each occurrence is a group containing delocalizedπ-electrons through which K is bound to M, said K group containing up to50 atoms not counting hydrogen atoms, optionally two or more K groupsmay be joined together forming a bridged structure, and furtheroptionally one or more K groups may be bound to Z, to X or to both Z andX;

X independently each occurrence is a monovalent, anionic moiety havingup to 40 non-hydrogen atoms, optionally one or more X groups may bebonded together thereby forming a divalent or polyvalent anionic group,and, further optionally, one or more X groups and one or more Z groupsmay be bonded together thereby forming a moiety that is both covalentlybound to M and coordinated thereto;

Z independently each occurrence is a neutral, Lewis base donor ligand ofup to 50 non-hydrogen atoms containing at least one unshared electronpair through which Z is coordinated to M;

k is an integer from 0 to 3;

x is an integer from 1 to 4;

z is a number from 0 to 3; and

the sum, k+x, is equal to the formal oxidation state of M.

Suitable metal complexes include those containing from 1 to 3 π-bondedanionic or neutral ligand groups, which may be cyclic or non-cyclicdelocalized π-bonded anionic ligand groups. Exemplary of such π-bondedgroups are conjugated or nonconjugated, cyclic or non-cyclic diene anddienyl groups, allyl groups, boratabenzene groups, phosphole, and arenegroups. By the term “π-bonded” is meant that the ligand group is bondedto the transition metal by a sharing of electrons from a partiallydelocalized π-bond.

Each atom in the delocalized π-bonded group may independently besubstituted with a radical selected from the group consisting ofhydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substitutedheteroatoms wherein the heteroatom is selected from Group 14-16 of thePeriodic Table of the Elements, and such hydrocarbyl-substitutedheteroatom radicals further substituted with a Group 15 or 16 heteroatom containing moiety. In addition two or more such radicals maytogether form a fused ring system, including partially or fullyhydrogenated fused ring systems, or they may form a metallocycle withthe metal. Included within the term “hydrocarbyl” are C₁₋₂₀ straight,branched and cyclic alkyl radicals, C₆₋₂₀ aromatic radicals, C₇₋₂₀alkyl-substituted aromatic radicals, and C₇₋₂₀ aryl-substituted alkylradicals. Suitable hydrocarbyl-substituted heteroatom radicals includemono-, di- and tri-substituted radicals of boron, silicon, germanium,nitrogen, phosphorus or oxygen wherein each of the hydrocarbyl groupscontains from 1 to 20 carbon atoms. Examples include N,N-dimethylamino,pyrrolidinyl, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl,methyldi(t-butyl)silyl, triphenylgermyl, and trimethylgermyl groups.Examples of Group 15 or 16 hetero atom containing moieties includeamino, phosphino, alkoxy, or alkylthio moieties or divalent derivativesthereof, for example, amide, phosphide, alkyleneoxy or alkylenethiogroups bonded to the transition metal or Lanthanide metal, and bonded tothe hydrocarbyl group, π-bonded group, or hydrocarbyl-substitutedheteroatom.

Examples of suitable anionic, delocalized π-bonded groups includecyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl,tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl,dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups,phosphole, and boratabenzyl groups, as well as inertly substitutedderivatives thereof, especially C₁₋₁₀ hydrocarbyl-substituted ortris(C₁₋₁₀ hydrocarbyl)silyl-substituted derivatives thereof. Preferredanionic delocalized π-bonded groups are cyclopentadienyl,pentamethylcyclopentadienyl, tetramethylcyclopentadienyl,tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl,fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl,tetrahydrofluorenyl, octahydrofluorenyl, 1-indacenyl,3-pyrrolidinoinden-1-yl, 3,4-(cyclopenta(l)phenanthren-1-yl, andtetrahydroindenyl.

The boratabenzyl ligands are anionic ligands which are boron containinganalogues to benzene. They are previously known in the art having beendescribed by G. Herberich, et al., in Organometallics, 14, 1, 471-480(1995). Preferred boratabenzenes correspond to the formula:

wherein R¹ is an inert substituent, preferably selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, halo or germyl, said lehaving up to 20 atoms not counting hydrogen, and optionally two adjacentR¹ groups may be joined together. In complexes involving divalentderivatives of such delocalized m-bonded groups one atom thereof isbonded by means of a covalent bond or a covalently bonded divalent groupto another atom of the complex thereby forming a bridged system.

Phospholes are anionic ligands that are phosphorus containing analoguesto a cyclopentadienyl group. They are previously known in the art havingbeen described by WO 98/50392, and elsewhere. Preferred phospholeligands correspond to the formula:

wherein R¹ is as previously defined.

Preferred transition metal complexes for use herein correspond to theformula: MK_(k)X_(x)Z_(z), or a dimer thereof, wherein:

M is a Group 4 metal;

K is a group containing delocalized m-electrons through which K is boundto M, said K group containing up to 50 atoms not counting hydrogenatoms, optionally two K groups may be joined together forming a bridgedstructure, and further optionally one K may be bound to X or Z;

X each occurrence is a monovalent, anionic moiety having up to 40non-hydrogen atoms, optionally one or more X and one or more K groupsare bonded together to form a metallocycle, and further optionally oneor more X and one or more Z groups are bonded together thereby forming amoiety that is both covalently bound to M and coordinated thereto;

Z independently each occurrence is a neutral, Lewis base donor ligand ofup to 50 non-hydrogen atoms containing at least one unshared electronpair through which Z is coordinated to M;

k is an integer from 0 to 3;

x is an integer from 1 to 4;

z is a number from 0 to 3; and

the sum, k+x, is equal to the formal oxidation state of M.

Preferred complexes include those containing either one or two K groups.The latter complexes include those containing a bridging group linkingthe two K groups. Preferred bridging groups are those corresponding tothe formula (ER′₂)_(e) wherein E is silicon, germanium, tin, or carbon,R′ independently each occurrence is hydrogen or a group selected fromsilyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R′having up to 30 carbon or silicon atoms, and e is 1 to 8. Preferably, R′independently each occurrence is methyl, ethyl, propyl, benzyl,tert-butyl, phenyl, methoxy, ethoxy or phenoxy.

Examples of the complexes containing two K groups are compoundscorresponding to the formula:

wherein:

M is titanium, zirconium or hafnium, preferably zirconium or hafnium, inthe +2 or +4 formal oxidation state;

R³ in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R³ having up to 20 non-hydrogen atoms, oradjacent R³ groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system, and

X″ independently each occurrence is an anionic ligand group of up to 40non-hydrogen atoms, or two X″ groups together form a divalent anionicligand group of up to 40 non-hydrogen atoms or together are a conjugateddiene having from 4 to 30 non-hydrogen atoms bound by means ofdelocalized π-electrons to M, whereupon M is in the +2 formal oxidationstate, and

R′, E and e are as previously defined.

Exemplary bridged ligands containing two π-bonded groups are:dimethylbis(cyclopentadienyl)silane,dimethylbis(tetramethylcyclopentadienyl)silane,dimethylbis(2-ethylcyclopentadien-1-yl)silane,dimethylbis(2-t-butylcyclopentadien-1-yl)silane,2,2-bis(tetramethylcyclopentadienyl)propane,dimethylbis(inden-1-yl)silane, dimethylbis(tetrahydroinden-1-yl)silane,dimethylbis(fluoren-1-yl)silane,dimethylbis(tetrahydrofluoren-1-yl)silane,dimethylbis(2-methyl-4-phenylinden-1-yl)-silane,dimethylbis(2-methylinden-1-yl)silane,dimethyl(cyclopentadienyl)(fluoren-1-yl)silane,dimethyl(cyclopentadienyl)(octahydrofluoren-1-yl)silane,dimethyl(cyclopentadienyl)(tetrahydrofluoren-1-yl)silane,(1,1,2,2-tetramethy)-1,2-bis(cyclopentadienyl)disilane,(1,2-bis(cyclopentadienyl)ethane, anddimethyl(cyclopentadienyl)-1-(fluoren-1-yl)methane.

Preferred X″ groups are selected from hydride, hydrocarbyl, silyl,germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl andaminohydrocarbyl groups, or two X″ groups together form a divalentderivative of a conjugated diene or else together they form a neutral,π-bonded, conjugated diene. Most preferred X″ groups are C₁₋₂₀hydrocarbyl groups.

Examples of metal complexes of the foregoing formula suitable for use inthe present invention include:

-   bis(cyclopentadienyl)zirconiumdimethyl,-   bis(cyclopentadienyl)zirconium dibenzyl,-   bis(cyclopentadienyl)zirconium methyl benzyl,-   bis(cyclopentadienyl)zirconium methyl phenyl,-   bis(cyclopentadienyl)zirconiumdiphenyl,-   bis(cyclopentadienyl)titanium-allyl,-   bis(cyclopentadienyl)zirconiummethylmethoxide,-   bis(cyclopentadienyl)zirconiummethylchloride,-   bis(pentamethylcyclopentadienyl)zirconiumdimethyl,-   bis(pentamethylcyclopentadienyl)titaniumdimethyl,-   bis(indenyl)zirconiumdimethyl,-   indenylfluorenylzirconiumdimethyl,-   bis(indenyl)zirconiummethyl(2-(dimethylamino)benzyl),-   bis(indenyl)zirconiummethyltrimethylsilyl,-   bis(tetrahydroindenyl)zirconiummethyltrimethylsilyl,-   bis(pentamethylcyclopentadienyl)zirconiummethylbenzyl,-   bis(pentamethylcyclopentadienyl)zirconiumdibenzyl,-   bis(pentamethylcyclopentadienyl)zirconiummethylmethoxide,-   bis(pentamethylcyclopentadienyl)zirconiummethylchloride,-   bis(methylethylcyclopentadienyl)zirconiumdimethyl,-   bis(butylcyclopentadienyl)zirconiumdibenzyl,-   bis(t-butylcyclopentadienyl)zirconiumdimethyl,-   bis(ethyltetramethylcyclopentadienyl)zirconiumdimethyl,-   bis(methylpropylcyclopentadienyl)zirconiumdibenzyl,-   bis(trimethylsilylcyclopentadienyl)zirconiumdibenzyl,-   dimethylsilylbis(cyclopentadienyl)zirconiumdimethyl,-   dimethylsilylbis(tetramethylcyclopentadienyl)titanium (III) allyl-   dimethylsilylbis(t-butylcyclopentadienyl)zirconiumdichloride,-   dimethylsilylbis(n-butylcyclopentadienyl)zirconiumdichloride,-   (methylenebis(tetramethylcyclopentadienyl)titanium(III)    2-(dimethylamino)benzyl,-   (methylenebis(n-butylcyclopentadienyl)titanium(III)    2-(dimethylamino)benzyl,-   dimethylsilylbis(indenyl)zirconiumbenzylchloride,-   dimethylsilylbis(2-methylindenyl)zirconiumdimethyl,-   dimethylsilylbis(2-methyl-4-phenylindenyl)zirconiumdimethyl,-   dimethylsilylbis(2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadiene,-   dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium (II)    1,4-diphenyl-1,3-butadiene,-   dimethylsilylbis(tetrahydroindenyl)zirconium(II)    1,4-diphenyl-1,3-butadiene,-   dimethylsilylbis(tetramethylcyclopentadienyl)zirconium dimethyl-   dimethylsilylbis(fluorenyl)zirconiumdimethyl,-   dimethylsilyl-bis(tetrahydrofluorenyl)zirconium bis(trimethylsilyl),-   (isopropylidene)(cyclopentadienyl)(fluorenyl)zirconiumdibenzyl, and-   dimethylsilyl(tetramethylcyclopentadienyl)(fluorenyl)zirconium    dimethyl.

A further class of metal complexes utilized in the present inventioncorresponds to the preceding formula: MKZ_(z)X_(x), or a dimer thereof,wherein M, K, X, x and z are as previously defined, and Z is asubstituent of up to 50 non-hydrogen atoms that together with K forms ametallocycle with M.

Preferred Z substituents include groups containing up to 30 non-hydrogenatoms comprising at least one atom that is oxygen, sulfur, boron or amember of Group 14 of the Periodic Table of the Elements directlyattached to K, and a different atom, selected from the group consistingof nitrogen, phosphorus, oxygen or sulfur that is covalently bonded toM.

More specifically this class of Group 4 metal complexes used accordingto the present invention includes “constrained geometry catalysts”corresponding to the formula:

wherein:

M is titanium or zirconium, preferably titanium in the +2, +3, or +4formal oxidation state;

K¹ is a delocalized, π-bonded ligand group optionally substituted withfrom 1 to 5 R² groups,

R² in each occurrence independently is selected from the groupconsisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo andcombinations thereof, said R² having up to 20 non-hydrogen atoms, oradjacent R² groups together form a divalent derivative (that is, ahydrocarbadiyl, siladiyl or germadiyl group) thereby forming a fusedring system,

each X is a halo, hydrocarbyl, hydrocarbyloxy or silyl group, said grouphaving up to 20 non-hydrogen atoms, or two X groups together form aneutral C₅₋₃₀ conjugated diene or a divalent derivative thereof;

Y is —O—, —S—, —NR′—, —PR′—; and

X′ is SiR′₂, CR′₂, SiR′₂SiR′₂, CR′₂CR′₂, CR′═CR′, CR′₂SiR′₂, or GeR′₂,and

R′ independently each occurrence is hydrogen or a group selected fromsilyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R′having up to 30 carbon or silicon atoms.

Specific examples of the foregoing constrained geometry metal complexesinclude compounds corresponding to the formula:

wherein,

Ar is an aryl group of from 6 to 30 atoms not counting hydrogen;

R⁴ independently each occurrence is hydrogen, Ar, or a group other thanAr selected from hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl,halide, hydrocarbyloxy, trihydrocarbylsiloxy,bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino,hydrocarbadiylamino, hydrocarbylimino, di(hydrocarbyl)phosphino,hydrocarbadiylphosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl,trihydrocarbylsilyl-substituted hydrocarbyl,trihydrocarbylsiloxy-substituted hydrocarbyl,bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R group having up to 40atoms not counting hydrogen atoms;

M is titanium;

X′ is SiR⁶ ₂, CR⁶ ₂, SiR⁶ ₂SiR⁶ ₂, CR⁶ ₂CR⁶ ₂, CR⁶═CR⁶, CR⁶ ₂SiR⁶ ₂,BR⁶, BR⁶L″, or GeR⁶ ₂;

Y is —O—, —S—, —PR⁵—; —NR⁵ ₂, or —PR⁵ ₂;

R⁵, independently each occurrence, is hydrocarbyl, trihydrocarbylsilyl,or trihydrocarbylsilylhydrocarbyl, said R⁵ having up to 20 atoms otherthan hydrogen, and optionally two R⁵ groups or R⁵ together with Y or Zform a ring system;

R⁶, independently each occurrence, is hydrogen, or a member selectedfrom hydrocarbyl, hydrocarbyloxy, silyl, halogenated alkyl, halogenatedaryl, —NR⁵ ₂, and combinations thereof, said R⁶ having up to 20non-hydrogen atoms, and optionally, two R⁶ groups or R⁶ together with Zforms a ring system;

Z is a neutral diene or a monodentate or polydentate Lewis baseoptionally bonded to R⁵, R⁶, or X;

X is hydrogen, a monovalent anionic ligand group having up to 60 atomsnot counting hydrogen, or two X groups are a divalent ligand group;

x is 1 or 2; and

z is 0, 1 or 2.

Preferred examples of the foregoing metal complexes are substituted atboth the 3- and 4-positions of a cyclopentadienyl or indenyl group withan Ar group.

Examples of the foregoing metal complexes include:

-   (3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,3-diphenyl-1,3-butadiene;-   (3-(pyrrol-1-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(pyrrol-1-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-(pyrrol-1-yl)cyclopentadien-1-yl))dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3,4-diphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,3-pentadiene;-   (3-(3-N,N-dimethylamino)phenyl)cyclopentadien-1-yl)-dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(3-N,N-dimethylamino)phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-(3-N,N-dimethylamino)phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-(4-methoxyphenyl)-4-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-(4-methoxyphenyl)-4-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-(4-methoxyphenyl)-4-phenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-phenyl-4-methoxycyclopentadien-1-yl)-dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenyl-4-methoxycyclopentadien-1-yl)-dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenyl-4-methoxycyclopentadien-1-yl)-dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   2-methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   ((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silane    titanium dichloride,-   ((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silane    titanium dimethyl,-   ((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl,-   (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene;-   (2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dichloride,-   (2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium    dimethyl, and-   (2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(t-butylamido)silanetitanium (II)    1,4-diphenyl-1,3-butadiene.

Additional examples of suitable metal complexes for use as catalystsherein are polycyclic complexes corresponding to the formula:

where M is titanium in the +2, +3 or +4 formal oxidation state;

R⁷ independently each occurrence is hydride, hydrocarbyl, silyl, germyl,halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino,di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino,hydrocarbylene-phosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substitutedhydrocarbyl, hydrocarbylsiloxy-substituted hydrocarbyl,hydrocarbylsilylamino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylene-phosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R⁷ group having up to40 atoms not counting hydrogen, and optionally two or more of theforegoing groups may together form a divalent derivative;

R⁸ is a divalent hydrocarbylene- or substituted hydrocarbylene groupforming a fused system with the remainder of the metal complex, said R⁸containing from 1 to 30 atoms not counting hydrogen;

X′ is a divalent moiety, or a moiety comprising one σ-bond and a neutraltwo electron pair able to form a coordinate-covalent bond to M, said X′comprising boron, or a member of Group 14 of the Periodic Table of theElements, and also comprising nitrogen, phosphorus, sulfur or oxygen;

X is a monovalent anionic ligand group having up to 60 atoms exclusiveof the class of ligands that are cyclic, delocalized, π-bound ligandgroups and optionally two X groups together form a divalent ligandgroup;

Z independently each occurrence is a neutral ligating compound having upto 20 atoms;

x is 0, 1 or 2; and

z is zero or 1.

Preferred examples of such complexes are 3-phenyl-substituteds-indecenyl complexes corresponding to the formula:

2,3-dimethyl-substituted s-indecenyl complexes corresponding to theformulas:

or 2-methyl-substituted s-indecenyl complexes corresponding to theformula:

Additional examples of metal complexes that are usefully employed ascatalyst (A) according to the present invention include those of theformula:

Specific metal complexes include:

-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (II) 1,4-diphenyl-1,3-butadiene,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (II) 1,3-pentadiene,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (III) 2-(N,N-dimethylamino)benzyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dichloride,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dimethyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dibenzyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (II) 1,4-diphenyl-1,3-butadiene,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (II) 1,3-pentadiene,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (III) 2-(N,N-dimethylamino)benzyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dichloride,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dimethyl,-   (8-difluoro    methylene-1,8-dihydrodibenzo[e,h]azulen-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dibenzyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (II) 1,4-diphenyl-1,3-butadiene,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (II) 1,3-pentadiene,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (III) 2-(N,N-dimethylamino)benzyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dichloride,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dimethyl,-   (8-methylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dibenzyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (II) 1,4-diphenyl-1,3-butadiene,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (II) 1,3-pentadiene,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (III) 2-(N,N-dimethylamino)benzyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dichloride,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dimethyl,-   (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulen-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide    titanium (IV) dibenzyl, and mixtures thereof, especially mixtures of    positional isomers.

Further illustrative examples of metal complexes for use according tothe present invention correspond to the formula:

where M is titanium in the +2, +3 or +4 formal oxidation state;

T is —NR⁹— or —O—;

R⁹ is hydrocarbyl, silyl, germyl, dihydrocarbylboryl, or halohydrocarbylor up to 10 atoms not counting hydrogen;

R¹⁰ independently each occurrence is hydrogen, hydrocarbyl,trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, germyl, halide,hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino,di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino,hydrocarbylene-phosphino, hydrocarbylsulfido, halo-substitutedhydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substitutedhydrocarbyl, hydrocarbylsiloxy-substituted hydrocarbyl,hydrocarbylsilylamino-substituted hydrocarbyl,di(hydrocarbyl)amino-substituted hydrocarbyl,hydrocarbyleneamino-substituted hydrocarbyl,di(hydrocarbyl)phosphino-substituted hydrocarbyl,hydrocarbylenephosphino-substituted hydrocarbyl, orhydrocarbylsulfido-substituted hydrocarbyl, said R¹⁰ group having up to40 atoms not counting hydrogen atoms, and optionally two or more of theforegoing adjacent R¹⁰ groups may together form a divalent derivativethereby forming a saturated or unsaturated fused ring;

X′ is a divalent moiety lacking in delocalized m-electrons, or such amoiety comprising one σ-bond and a neutral two electron pair able toform a coordinate-covalent bond to M, said X′ comprising boron, or amember of Group 14 of the Periodic Table of the Elements, and alsocomprising nitrogen, phosphorus, sulfur or oxygen;

X is a monovalent anionic ligand group having up to 60 atoms exclusiveof the class of ligands that are cyclic ligand groups bound to M throughdelocalized m-electrons or two X groups together are a divalent anionicligand group;

Z independently each occurrence is a neutral ligating compound having upto 20 atoms;

x is 0, 1, 2, or 3; and

z is 0 or 1.

Highly preferably T is —N(CH₃), X is halo or hydrocarbyl, x is 2, X′ isdimethylsilane, z is 0, and R¹⁰ each occurrence is hydrogen, ahydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, hydrocarbyleneamino,dihydrocarbylamino-substituted hydrocarbyl group, orhydrocarbyleneamino-substituted hydrocarbyl group of up to 20 atoms notcounting hydrogen, and optionally two R¹⁰ groups may be joined together.

Illustrative metal complexes of the foregoing formula that may beemployed in the practice of the present invention further include thefollowing compounds:

-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)    silanetitanium (II) 1,4-diphenyl-1,3-butadiene,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)    silanetitanium (II) 1,3-pentadiene,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)    silanetitanium (III) 2-(N,N-dimethylamino)benzyl,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)    silanetitanium (IV) dichloride,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)    silanetitanium (IV) dimethyl,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)    silanetitanium (IV) dibenzyl,-   (t-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)    silanetitanium (IV) bis(trimethylsilyl),-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,3-pentadiene,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (III)    2-(N,N-dimethylamino)benzyl,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dichloride,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dimethyl,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dibenzyl,-   (cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    bis(trimethylsilyl),-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,3-pentadiene,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (III)    2-(N,N-dimethylamino)benzyl,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dichloride,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dimethyl,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dibenzyl,-   (t-butylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    bis(trimethylsilyl),-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (II)    1,3-pentadiene,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (III)    2-(N,N-dimethylamino)benzyl,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dichloride,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dimethyl,-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    dibenzyl; and-   (cyclohexylamido)di(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-indene-2-yl)silanetitanium (IV)    bis(trimethylsilyl).

Illustrative Group 4 metal complexes that may be employed in thepractice of the present invention further include:

-   (tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,-   (tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitaniumdimethyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)    dimethylsilanetitanium dibenzyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienypdimethylsilanetitanium    dimethyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)-1,2-ethanediyltitanium    dimethyl,-   (tert-butylamido)(tetramethyl-η⁵-indenyl)dimethylsilanetitanium    dimethyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilane    titanium (III)-   2-(dimethylamino)benzyl;    (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (III)    allyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (III)    2,4-dimethylpentadienyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (II)    1,3-pentadiene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)    2,4-hexadiene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)    2,3-dimethyl-1,3-butadiene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)    isoprene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)    1,3-butadiene,-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)    2,3-dimethyl-1,3-butadiene,-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)    isoprene-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)    dimethyl    (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)    dibenzyl-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (IV)    1,3-butadiene,-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II)    1,3-pentadiene,-   (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (II)    1,3-pentadiene,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)    dimethyl,-   (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium (IV)    dibenzyl,-   (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II)    1,4-diphenyl-1,3-butadiene,-   (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II)    1,3-pentadiene,-   (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium (II)    2,4-hexadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (IV)    1,3-butadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (IV)    2,3-dimethyl-1,3-butadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (IV)    isoprene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (II)    1,4-dibenzyl-1,3-butadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethylsilanetitanium (II)    2,4-hexadiene,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl)dimethyl-silanetitanium (II)    3-methyl-1,3-pentadiene,-   (tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitaniumdimethyl,-   (tert-butylamido)(6,6-dimethylcyclohexadienyl)dimethylsilanetitaniumdimethyl,-   (tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl,-   (tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitaniumdimethyl-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl    methylphenylsilanetitanium (IV) dimethyl,-   (tert-butylamido)(tetramethyl-η⁵-cyclopentadienyl    methylphenylsilanetitanium (II) 1,4-diphenyl-1,3-butadiene,-   1-(tert-butylamido)-2-(tetramethyl-re-cyclopentadienyl)ethanediyltitanium (IV)    dimethyl, and-   1-(tert-butylamido)-2-(tetramethyl-re-cyclopentadienyl)ethanediyl-titanium (II)    1,4-diphenyl-1,3-butadiene.

Other delocalized, π-bonded complexes, especially those containing otherGroup 4 metals, will, of course, be apparent to those skilled in theart, and are disclosed among other places in: WO 03/78480, WO 03/78483,WO 02/92610, WO 02/02577, US 2003/0004286 and U.S. Pat. Nos. 6,515,155,6,555,634, 6,150,297, 6,034,022, 6,268,444, 6,015,868, 5,866,704, and5,470,993.

The polyvalent Lewis base complexes for use in the present inventionalso include Group 4 metal derivatives, especially hafnium derivativesof hydrocarbylamine substituted heteroaryl compounds, especiallycompounds of the formula R¹¹HN-T-R¹². Preferably the complexescorrespond to the formula:

wherein:

R¹¹ is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl,aryl, and inertly substituted derivatives thereof containing from 1 to30 atoms not counting hydrogen;

T¹ is a divalent bridging group of from 1 to 20 atoms other thanhydrogen, preferably a mono- or di-C₁₋₂₀ hydrocarbyl substitutedmethylene or silane group; and

R¹² is a C₆₋₂₀ heteroaryl group containing Lewis base functionality,especially a pyridin-2-yl- or substituted pyridin-2-yl group;

R¹² and in the metal complex, M¹ is a Group 4 metal, preferably hafnium;

X¹ is an anionic, neutral or dianionic ligand group;

x′ is a number from 0 to 5 indicating the number of such X¹ groups; and

bonds, optional bonds and electron donative interactions are representedby lines, dotted lines and arrows respectively.

Preferred complexes are those wherein ligand formation results fromhydrogen elimination from the amine group and optionally from the lossof one or more additional groups, especially from R¹². In addition,electron donation from the Lewis base functionality, preferably anelectron pair, provides additional stability to the metal center.Preferred examples of the foregoing polyfunctional Lewis base compoundsand the resulting metal complexes correspond to the formulas:

wherein

M¹, X¹, x′, R¹¹ and T¹ are as previously defined,

R¹³, R¹⁴, R¹⁵ and R¹⁶ are hydrogen, halo, or an alkyl, cycloalkyl,heteroalkyl, heterocycloalkyl, aryl, or silyl group of up to 20 atomsnot counting hydrogen, or adjacent R¹³, R¹⁴, R¹⁵ or R¹⁶ groups may bejoined together thereby forming fused ring derivatives, and

bonds, optional bonds and electron pair donative interactions arerepresented by lines, dotted lines and arrows respectively.

More preferred examples of the foregoing difunctional Lewis basecompounds and metal complexes correspond to the formula:

wherein

M¹, X¹, and x′ are as previously defined,

R¹³, R¹⁴, R¹⁵ and R¹⁶ are as previously defined, preferably R¹³, R¹⁴,and R¹⁵ are hydrogen, or C₁₋₄ alkyl, and R¹⁶ is C₆₋₂₀ aryl, mostpreferably naphthalenyl;

R^(a) independently each occurrence is C₁₋₄ alkyl, and a is 1-5, mostpreferably le in two ortho-positions is isopropyl or t-butyl;

R¹⁷ and R¹⁸ independently each occurrence are hydrogen, halogen, or aC₁₋₂₀ alkyl or aryl group, most preferably one of R¹⁷ and R¹⁸ ishydrogen and the other is a C₆₋₂₀ aryl group, especially a fusedpolycyclic aryl group, most preferably an anthracenyl group, and

bonds, optional bonds and electron pair donative interactions arerepresented by lines, dotted lines and arrows respectively.

Highly preferred polyfunctional Lewis base compounds and metal complexesfor use herein correspond to the formula:

wherein X¹ each occurrence is halide, N,N-dimethylamido, or C₁₋₄ alkyl,and preferably each occurrence X is methyl;

R^(b) independently each occurrence is hydrogen, halogen, C₁₋₂₀ alkyl,or C₆₋₂₀ aryl, or two adjacent R^(b) groups are joined together therebyforming a ring, and b is 1-5; and

R^(c) independently each occurrence is hydrogen, halogen, C₁₋₂₀ alkyl,or C₆₋₂₀ aryl, or two adjacent R^(c) groups are joined together therebyforming a ring, and c is 1-5.

Most highly preferred examples of metal complexes for use according tothe present invention are complexes of the following formulas:

wherein R^(x) is C₁₋₄ alkyl or cycloalkyl, preferably methyl orisopropyl; and

X¹ each occurrence is halide, N,N-dimethylamido, or C₁₋₄ alkyl,preferably methyl.

Specific examples of such metal complexes include:

-   [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dimethyl;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    di(N,N-dimethylamido);-   [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dichloride;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dimethyl;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    di(N,N-dimethylamido);-   [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dichloride;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dimethyl;-   [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    di(N,N-dimethylamido); and-   [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafnium    dichloride.

Under the reaction conditions used to prepare the metal complexes usedin the present invention, it has been discovered that the hydrogen ofthe 2-position of the α-naphthalene group substituted at the 6-positionof the pyridin-2-yl group is subject to elimination, thereby uniquelyforming metal complexes wherein the metal is covalently bonded to boththe resulting amide group and to the 2-position of the α-naphthalenylgroup, as well as stabilized by coordination to the pyridinyl nitrogenatom through the electron pair of the nitrogen atom.

The foregoing polyvalent Lewis base complexes are conveniently preparedby standard metallation and ligand exchange procedures involving asource of the transition metal and the neutral polyfunctional ligandsource. The complexes may also be prepared by means of an amideelimination and hydrocarbylation process starting from the correspondingGroup 4 metal tetraamide and a hydrocarbylating agent, such astrimethylaluminum. Other techniques may be used as well. These complexesare known from the disclosures of, U.S. Pat. Nos. 6,320,005 and6,103,657, PCT publications WO 02/38628 and WO 03/40195, and U.S. Ser.No. 10/429,024, filed May 2, 2003.

Suitable metal compounds additional include Group 4-10 derivativescorresponding to the formula:

wherein

-   -   M² is a metal of Groups 4-10 of the Periodic Table of the        elements, preferably Group 4, Ni(II) or Pd(II), most preferably        zirconium or hafnium;    -   T² independently each occurrence is a nitrogen, oxygen or        phosphorus containing group;    -   X² is halo, hydrocarbyl, or hydrocarbyloxy;    -   t is one or two;    -   x″ is a number selected to provide charge balance;    -   and T² and N are linked by a bridging ligand.

Such catalysts have been previously disclosed in J. Am. Chem. Soc., 118,267-268 (1996), J. Am. Chem. Soc., 117, 6414-6415 (1995), andOrganometallics, 16, 1514-1516, (1997), among other disclosures.

Preferred examples of the foregoing metal complexes are aromatic diimineor aromatic dioxyimine complexes of Group 4 metals, especiallyzirconium, corresponding to the formula:

wherein;

M², X² and T² are as previously defined;

R^(d) independently each occurrence is hydrogen, halogen, or R^(e); and

R^(e) independently each occurrence is C₁₋₁₀ hydrocarbyl, preferablyC₁₋₄ alkyl.

Additional suitable metal complexes for use herein include derivativesof Group 6 metals, especially compounds corresponding to the formula:M³(OR^(f))_(u)(NR^(f) ₂)_(r)X³ _(v-u-r)

wherein M³ is a Group 6 metal, especially chromium in the +3 formaloxidation state;

R^(f) independently in each occurrence is an alkyl group of from 3 to 20carbons, a cycloalkyl group of from 5 to 20 carbons, an aryl oralkylaryl group of from 6 to 20 carbons, or a tri(C₁₋₂₀)hydrocarbylsilylgroup, and optionally two R^(f) groups on the same or adjacent amidegroups may be joined together thereby forming a heterocycloaliphaticring, or an alkyl-, aryl-, cycloalkyl-, ortrihydrocarbylsilyl-substituted derivative thereof;

X³ is an anionic ligand of up to 20 atoms not counting hydrogen, andoptionally one or more X³ groups and/or one or more OR^(f) or NR^(f) ₂groups may be joined together to form an aliphatic or aromatic ring,

u and r are numbers greater than or equal to 0 and less than or equal tov, and

v is the valence of M³.

Preferred R^(f) groups include secondary or tertiary alkyl groups, aryl,alkylaryl, and trihydrocarbylsilyl groups of from 3 to 20 carbons, ortwo R^(f) groups on a single amide together are a C₅₋₁₂ alkylene group.Most preferably R^(f) each occurrence is isopropyl, cyclohexyl ortrimethylsilyl.

Preferred X³ groups include hydride, halide, hydrocarbyl,trihydrocarbylsilyl, hydrocarbyloxy, and trihydrocarbylsiloxy of up to10 atoms not counting hydrogen, most preferably chloride or methyl.

Additional examples of suitable Group 6 metal compounds include chromiumtris(bis(trimethylsilyl)amide), chromium tris(diisopropylamide),chromium tris(diphenylamide), chromium tris(di(2-methylphenyl)amide),chromium tris(dicyclohexylamide), and chromiumtris(2,2,6,6-tetramethylpiperdyl). Preferred Group 6 metal compounds arechromium tris(bis(trimethylsilyl)amide) and chromiumtris(diisopropylamide). The group 6 metal compounds may be readilyprepared by reaction of the corresponding trialkyl chromium compoundwith the metallated salt of the desired ligand in an ether solventfollowed by recovery from an aliphatic hydrocarbon, by the techniquepreviously disclosed in J.C.S., Dalton, (1972), p 1580-1584, or by anyother suitable technique.

Additional suitable compounds include metal complexes of hydroxyarylsubstituted bis(aryloxy) ligands of the formula: (HOAr²O)₂T³.Preferably, such complexes correspond to the formula:

wherein:

T³ is a divalent bridging group of from 2 to 20 atoms not countinghydrogen, preferably a substituted or unsubstituted, C₃₋₆ alkylenegroup; and

Ar² independently each occurrence is a C₆₋₂₀ arylene or inertlysubstituted arylene group;

M¹ is a Group 4 metal, preferably hafnium;

X¹ is an anionic, neutral or dianionic ligand group;

x′ is a number from 0 to 5 indicating the number of such X¹ groups; and

bonds, optional bonds and electron donative interactions are representedby lines, dotted lines and arrows respectively.

Preferred examples of the foregoing metal complexes correspond to thefollowing formula:

where

-   -   Ar⁴ is C₆₋₂₀ aryl or inertly substituted derivatives thereof,        especially 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl,        dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl, and

T⁴ independently each occurrence is C₃₋₆ alkylene or an inertlysubstituted derivative thereof;

R¹⁴ independently each occurrence is hydrogen, halo, hydrocarbyl,trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl of up to 50 atomsnot counting hydrogen; and

X, independently each occurrence is halo or a hydrocarbyl ortrihydrocarbylsilyl group of up to 20 atoms not counting hydrogen, or 2×groups together are a divalent derivative of the foregoing hydrocarbylor trihydrocarbylsilyl groups.

Especially preferred are compounds of the formula:

wherein

-   -   Ar⁴ is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl,        dibenzo-1H-pyrrole-1-yl, or anthracen-5-yl,

R¹⁴ is hydrogen, halo, or C₁₋₄ alkyl, especially methyl

T⁴ is propan-1,3-diyl or butan-1,4-diyl, and

X is chloro, methyl or benzyl.

A most highly preferred metal compound corresponds to the formula:

Activator Compounds

The metal complexes are rendered catalytically active by combinationwith a cation forming cocatalyst, such as those previously known in theart for use with transition metal olefin polymerization complexes.Suitable cation forming cocatalysts for use herein include neutral Lewisacids, such as C₁₋₃₀ hydrocarbyl substituted Group 13 compounds,especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compoundsand halogenated (including perhalogenated) derivatives thereof, havingfrom 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbylgroup, more especially perfluorinated tri(aryl)boron compounds, and mostespecially tris(pentafluorophenyl)boron; nonpolymeric, compatible,noncoordinating, ion forming compounds (including the use of suchcompounds under oxidizing conditions), especially the use of ammonium-,phosphonium-, oxonium-, carbonium-, silylium- or sulfonium-salts ofcompatible, noncoordinating anions, or ferrocenium-, lead- or silversalts of compatible, noncoordinating anions; and combinations of theforegoing cation forming cocatalysts and techniques. The foregoingactivating cocatalysts and activating techniques have been previouslytaught with respect to different metal complexes for olefinpolymerizations in the following references: EP-A-277,003, U.S. Pat.Nos. 5,153,157, 5,064,802, 5,321,106, 5,721,185, 5,350,723, 5,425,872,5,625,087, 5,883,204, 5,919,983, 5,783,512, WO 99/15534, and WO99/42467.

Combinations of neutral Lewis acids, especially the combination of atrialkyl aluminum compound having from 1 to 4 carbons in each alkylgroup and a halogenated tri(hydrocarbyl)boron compound having from 1 to20 carbons in each hydrocarbyl group, especiallytris(pentafluorophenyl)boron, further combinations of such neutral Lewisacid mixtures with a polymeric or oligomeric alumoxane, and combinationsof a single neutral Lewis acid, especially tris(pentafluorophenyl)boronwith a polymeric or oligomeric alumoxane may be used as activatingcocatalysts. Preferred molar ratios of metalcomplex:tris(pentafluorophenylboron:alumoxane are from 1:1:1 to 1:5:20,more preferably from 1:1:1.5 to 1:5:10.

Suitable ion forming compounds useful as cocatalysts in one embodimentof the present invention comprise a cation which is a Bronsted acidcapable of donating a proton, and a compatible, noncoordinating anion,A⁻. As used herein, the term “noncoordinating” means an anion orsubstance which either does not coordinate to the transition metalcontaining precursor complex and the catalytic derivative derivedtherefrom, or which is only weakly coordinated to such complexes therebyremaining sufficiently labile to be displaced by a neutral Lewis base. Anoncoordinating anion specifically refers to an anion which whenfunctioning as a charge balancing anion in a cationic metal complex doesnot transfer an anionic substituent or fragment thereof to said cationthereby forming neutral complexes. “Compatible anions” are anions whichare not degraded to neutrality when the initially formed complexdecomposes and are noninterfering with desired subsequent polymerizationor other uses of the complex.

Preferred anions are those containing a single coordination complexcomprising a charge-bearing metal or metalloid core which anion iscapable of balancing the charge of the active catalyst species (themetal cation) which may be formed when the two components are combined.Also, said anion should be sufficiently labile to be displaced byolefinic, diolefinic and acetylenically unsaturated compounds or otherneutral Lewis bases such as ethers or nitriles. Suitable metals include,but are not limited to, aluminum, gold and platinum. Suitable metalloidsinclude, but are not limited to, boron, phosphorus, and silicon.Compounds containing anions which comprise coordination complexescontaining a single metal or metalloid atom are, of course, well knownand many, particularly such compounds containing a single boron atom inthe anion portion, are available commercially.

Preferably such cocatalysts may be represented by the following generalformula:(L*-H)_(g) ⁺(A)^(g−)wherein:

L* is a neutral Lewis base;

(L*-H)⁺ is a conjugate Bronsted acid of L*;

A^(g−) is a noncoordinating, compatible anion having a charge of g−, and

g is an integer from 1 to 3.

More preferably A^(g−) corresponds to the formula: [M′Q₄]⁻;

wherein:

M′ is boron or aluminum in the +3 formal oxidation state; and

Q independently each occurrence is selected from hydride, dialkylamido,halide, hydrocarbyl, hydrocarbyloxide, halosubstituted-hydrocarbyl,halosubstituted hydrocarbyloxy, and halo-substituted silylhydrocarbylradicals (including perhalogenated hydrocarbyl-perhalogenatedhydrocarbyloxy- and perhalogenated silylhydrocarbyl radicals), said Qhaving up to 20 carbons with the proviso that in not more than oneoccurrence is Q halide. Examples of suitable hydrocarbyloxide Q groupsare disclosed in U.S. Pat. No. 5,296,433.

In a more preferred embodiment, d is one, that is, the counter ion has asingle negative charge and is A⁻. Activating cocatalysts comprisingboron which are particularly useful in the preparation of catalysts ofthis invention may be represented by the following general formula:(L*-H)⁺(BQ₄)^(−;)wherein:

L* is as previously defined;

B is boron in a formal oxidation state of 3; and

Q is a hydrocarbyl-, hydrocarbyloxy-, fluorinated hydrocarbyl-,fluorinated hydrocarbyloxy-, or fluorinated silylhydrocarbyl-group of upto 20 nonhydrogen atoms, with the proviso that in not more than oneoccasion is Q hydrocarbyl.

Preferred Lewis base salts are ammonium salts, more preferablytrialkylammonium salts containing one or more C₁₂₋₄₀ alkyl groups. Mostpreferably, Q is each occurrence a fluorinated aryl group, especially, apentafluorophenyl group.

Illustrative, but not limiting, examples of boron compounds which may beused as an activating cocatalyst in the preparation of the improvedcatalysts of this invention are tri-substituted ammonium salts such as:

-   trimethylammonium tetrakis(pentafluorophenyl) borate,-   triethylammonium tetrakis(pentafluorophenyl) borate,-   tripropylammonium tetrakis(pentafluorophenyl) borate,-   tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate,-   tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate,-   N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate,-   N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate,-   N,N-dimethylanilinium benzyltris(pentafluorophenyl) borate,-   N,N-dimethylanilinium    tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl) borate,-   N,N-dimethylanilinium    tetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl) borate,-   N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl)    borate,-   N,N-diethylanilinium tetrakis(pentafluorophenyl) borate,-   N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)    borate,-   dimethyloctadecylammonium tetrakis(pentafluorophenyl) borate,-   methyldioctadecylammonium tetrakis(pentafluorophenyl) borate,    dialkyl ammonium salts such as:-   di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate,-   methyloctadecylammonium tetrakis(pentafluorophenyl) borate,-   methyloctadodecylammonium tetrakis(pentafluorophenyl) borate, and-   dioctadecylammonium tetrakis(pentafluorophenyl) borate;    tri-substituted phosphonium salts such as:-   triphenylphosphonium tetrakis(pentafluorophenyl) borate,-   methyldioctadecylphosphonium tetrakis(pentafluorophenyl) borate, and-   tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)    borate;    di-substituted oxonium salts such as:-   diphenyloxonium tetrakis(pentafluorophenyl) borate,-   di(o-tolyl)oxonium tetrakis(pentafluorophenyl) borate, and-   di(octadecyl)oxonium tetrakis(pentafluorophenyl) borate;    di-substituted sulfonium salts such as:-   di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and-   methylcotadecylsulfonium tetrakis(pentafluorophenyl) borate.

Preferred (L*-H)⁺ cations are methyldioctadecylammonium cations,dimethyloctadecylammonium cations, and ammonium cations derived frommixtures of trialkyl amines containing one or 2 C₁₄₋₁₈ alkyl groups.

Another suitable ion forming, activating cocatalyst comprises a salt ofa cationic oxidizing agent and a noncoordinating, compatible anionrepresented by the formula:(Ox^(h+))_(g)(A^(g−))_(h),wherein:

Ox^(h+) is a cationic oxidizing agent having a charge of h+;

h is an integer from 1 to 3; and

A^(g−) and g are as previously defined.

Examples of cationic oxidizing agents include: ferrocenium,hydrocarbyl-substituted ferrocenium, Ag^(+′) or Pb⁺². Preferredembodiments of Ag^(g−) are those anions previously defined with respectto the Bronsted acid containing activating cocatalysts, especiallytetrakis(pentafluorophenyl)borate.

Another suitable ion forming, activating cocatalyst comprises a compoundwhich is a salt of a carbenium ion and a noncoordinating, compatibleanion represented by the formula:[C]⁺A⁻wherein:

[C]⁺ is a C₁₋₂₀ carbenium ion; and

A⁻ is a noncoordinating, compatible anion having a charge of −1. Apreferred carbenium ion is the trityl cation, that istriphenylmethylium.

A further suitable ion forming, activating cocatalyst comprises acompound which is a salt of a silylium ion and a noncoordinating,compatible anion represented by the formula:(Q¹ ₃Si)⁺A⁻wherein:

Q¹ is C₁₋₁₀ hydrocarbyl, and A⁻ is as previously defined.

Preferred silylium salt activating cocatalysts are trimethylsilyliumtetrakispentafluorophenylborate, triethylsilyliumtetrakispentafluorophenylborate and ether substituted adducts thereof.Silylium salts have been previously generically disclosed in J. ChemSoc. Chem. Comm., 1993, 383-384, as well as Lambert, J. B., et al.,Organometallics, 1994, 13, 2430-2443. The use of the above silyliumsalts as activating cocatalysts for addition polymerization catalysts isdisclosed in U.S. Pat. No. 5,625,087.

Certain complexes of alcohols, mercaptans, silanols, and oximes withtris(pentafluorophenyl)boron are also effective catalyst activators andmay be used according to the present invention. Such cocatalysts aredisclosed in U.S. Pat. No. 5,296,433.

Suitable activating cocatalysts for use herein also include polymeric oroligomeric alumoxanes, especially methylalumoxane (MAO), triisobutylaluminum modified methylalumoxane (MMAO), or isobutylalumoxane; Lewisacid modified alumoxanes, especially perhalogenatedtri(hydrocarbyl)aluminum- or perhalogenated tri(hydrocarbyl)boronmodified alumoxanes, having from 1 to 10 carbons in each hydrocarbyl orhalogenated hydrocarbyl group, and most especiallytris(pentafluorophenyl)boron modified alumoxanes. Such cocatalysts arepreviously disclosed in U.S. Pat. Nos. 6,214,760, 6,160,146, 6,140,521,and 6,696,379.

A class of cocatalysts comprising non-coordinating anions genericallyreferred to as expanded anions, further disclosed in U.S. Pat. No.6,395,671, may be suitably employed to activate the metal complexes ofthe present invention for olefin polymerization. Generally, thesecocatalysts (illustrated by those having imidazolide, substitutedimidazolide, imidazolinide, substituted imidazolinide, benzimidazolide,or substituted benzimidazolide anions) may be depicted as follows:

wherein:

A*⁺ is a cation, especially a proton containing cation, and preferablyis a trihydrocarbyl ammonium cation containing one or two C₁₀₋₄₀ alkylgroups, especially a methyldi (C₁₄₋₂₀ alkyl)ammonium cation,

Q³, independently each occurrence, is hydrogen or a halo, hydrocarbyl,halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl, (includingmono-, di- and tri(hydrocarbyl)silyl) group of up to 30 atoms notcounting hydrogen, preferably C₁₋₂₀ alkyl, and

Q² is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)alumane).

Examples of these catalyst activators includetrihydrocarbylammonium-salts, especially, methyldi(C₁₄₋₂₀alkyl)ammonium-salts of:

-   bis(tris(pentafluorophenyl)borane)imidazolide,-   bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide,-   bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide,-   bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide,    bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide,    bis(tris(pentafluorophenyl)borane)imidazolinide,-   bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide,-   bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide,    bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide,    bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide,-   bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide,-   bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide,-   bis(tris(pentafluorophenyl)alumane)imidazolide,-   bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolide,-   bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide,    bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolide,    bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolide,-   bis(tris(pentafluorophenyl)alumane)imidazolinide,-   bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide,-   bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolinide,-   bis(tris(pentafluorophenyl)alumane)-4,5-bis(undecyl)imidazolinide,-   bis(tris(pentafluorophenyl)alumane)-4,5-bis(heptadecyl)imidazolinide,-   bis(tris(pentafluorophenyl)alumane)-5,6-dimethylbenzimidazolide, and-   bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyfibenzimidazolide.

Other activators include those described in PCT publication WO 98/07515such as tris(2,2′,2″-nonafluorobiphenyl) fluoroaluminate. Combinationsof activators are also contemplated by the invention, for example,alumoxanes and ionizing activators in combinations, see for example,EP-A-0 573120, PCT publications WO 94/07928 and WO 95/14044 and U.S.Pat. Nos. 5,153,157 and 5,453,410. WO 98/09996 describes activatingcatalyst compounds with perchlorates, periodates and iodates, includingtheir hydrates. WO 99/18135 describes the use of organoboroaluminumactivators. WO 03/10171 discloses catalyst activators that are adductsof Bronsted acids with Lewis acids. Other activators or methods foractivating a catalyst compound are described in for example, U.S. Pat.Nos. 5,849,852, 5,859,653, 5,869,723, EP-A-615981, and PCT publicationWO 98/32775. All of the foregoing catalyst activators as well as anyother know activator for transition metal complexes may be employedalone or in combination according to the present invention.

Polymerization Modifiers

The polymerization modifier (PM) compositions for use in the presentinvention in the most general sense comprise the reaction product of atleast two reagents, such as one or more Lewis acids with one or moreorganic protonating reagents. It should be appreciated by one of skillin the art that the resulting product may contain a mixture of species,including equilibria between various species and dynamic,interconverting compounds. In one embodiment of the invention, thereaction mixture formed upon combining the foregoing reagents in asuitable diluent, preferably a hydrocarbon such as hexane or heptane, ispreferred for use, rather than the purified and/or isolated reactionproduct itself.

Suitable Lewis acids are compounds of the formula: [M⁴A¹_(x′)G_(y′)]_(z′), wherein:

M⁴ is a metal of Groups 2-13, Ge, Sn, or Bi;

A¹ is independently an anionic or polyanionic ligand;

x′ is a number greater than zero and less than or equal to 6;

G is a neutral Lewis base, optionally bound to A¹;

y′ is a number from 0-4;

z′ is a number from 1 to 10.

Preferably, the Lewis acids are metal compounds of the general formula:M⁴A¹ _(x′)G_(y′), wherein M⁴ is a metal of Groups 2-13, Ge, Sn, or Bi;A¹ is independently an anionic ligand; x′ is an integer and is equal tothe valence of M⁴; G is a neutral Lewis base; and y′ is a number from0-4. More preferably, M⁴ is Mg, B, Ga, Al, or Zn; A¹ is C₁₋₂₀hydrocarbyl or inertly substituted hydrocarbyl, especially C₁₋₄₂ alkylor aryl. Preferred inert substituents include halide, trimethylsilyl,halo aryl, and halo alkyl.

The organic protonating reagents used in the present invention to formpolymerization modifiers include compounds of the formula:[(H-J¹)_(z″)A²]_(z′″), wherein:

J¹ is NA³, PA³, S, or O,

z″ is 1 or 2,

A² is C₁₋₂₀ hydrocarbyl or inertly substituted hydrocarbyl,tri(C₁₋₁₀hydrocarbyl)silyl, or a polyvalent derivative thereof,

A³ is hydrogen, C₁₋₂₀ hydrocarbyl or inertly substituted hydrocarbyl, ora covalent bond (when A² is a divalent ligand group and z″ is one); and

z′″ is a number from 1 to 10.

Preferred organic protonating reagents include compounds of the formula:(H-J¹)_(z″)A², wherein J¹ is NA³, PA³, S, or O, and z″ is 1 or 2; and A²is C₁₋₂₀ hydrocarbyl or inertly substituted hydrocarbyl,tri(C₁₋₄hydrocarbyl)silyl, or a divalent derivative thereof, especiallyC₁₋₁₂ alkyl, 1,4-butylene, tri(C₁₋₄alkyl)silyl, or aryl, and A³ ishydrogen, C₁₋₂₀ hydrocarbyl or inertly substituted hydrocarbyl, or acovalent bond. Preferred inert substituents are halide, trimethylsilyl,haloaryl, or haloalkyl.

By using a polymerization modifier according to the present invention,one or more process or product properties is beneficially affected.Examples include the ability to prepare copolymers of ethylene and oneor more comonomers, especially 1-butene, 4-methyl-1-pentene, 1-hexene,1-octene or styrene, having higher or lower comonomer incorporation atequivalent polymerization conditions or alternatively, preparingequivalent copolymers at higher polymerization temperatures or lowercomonomer concentrations in the reaction mixture. Another beneficialfeature of the use of a polymerization modifier may be greaterselectivity in product formation as determined by narrower or broadermolecular weight distribution (Mw/Mn) of homopolymers and copolymerproducts or a relative lack of formation or reduction in formation of aparticular species, such as a polymer fraction having differentiatedcrystallinity, solubility, tacticity, melting point, melt flow index,comonomer content, or other physical property. A further desirableresult of the use of a PM may be improved process properties such asimproved monomer conversion efficiency. Finally, in another embodiment,candidate PM materials may be evaluated based on performance undernon-standard reaction conditions. For example, due to specific reactantsor impurities in a reagent or monomer source, polymerization efficiencymay be adversely affected in the absence of a PM. Examples include theuse of comonomer, especially 1-octene, prepared by gasification(reaction of an H₂/H₂O mixture) with coal, peat, cellulose, or othercarbon source and fractionation of the resulting mixture.

In all of the foregoing examples it is desirable to apply statisticalevaluation tools to refine data generated by the individualpolymerizations or other reactions. In this manner, unreliable ordefective results can be eliminated and actual trends in the data morereadily identified. Desirably, data meeting statistically significantrequirements, especially data satisfying a 95 percent or greaterconfidence interval is used in the present invention. In addition, it isunderstood that optimum performance may be represented by a maximum orminimum value in a given property or result over a given interval(peaking profile) or alternatively, a steady, decreasing or increasingresult over the range of variables tested.

Often, in order to evaluate multiple candidates under slightly differentpolymerization conditions it is necessary to calculate conversion valuesunder standard reaction conditions based on a theoretical polymerizationmodel or on a separate result or variable derivable from such data.Thus, the variable of interest may also be selected based on suchtheoretical or calculated results, or by a combination of multiplevariables.

In addition to the polymerization modifier, conventional additives mayalso be employed in the reaction mixture to obtain one or morebeneficial results. For example, a scavenger may be employed to removedetrimental impurities, if any, present in the reaction mixture. Anexample of a suitable scavenger is an alumoxane compound, employed in anamount that is insufficient to result in activation of the metalcomplex. Especially preferred alumoxanes include triisopropylaluminummodified methylalumoxane or triisobutylaluminum modified methylalumoxaneavailable commercially under the trade designation MMAO-IP and MMAO-3Afrom Akzo Noble Corporation. Typically the molar quantity of suchscavenger employed ranges from 1 to 10 moles based on metal (aluminum)value per mole of metal complex.

The Selection Process

A “library” as the term is used herein means a group of compounds havingeither chemical diversity or process diversity. Chemical diversityrefers to a library having members that vary with respect to atoms ortheir arrangement in molecules or compounds. Process diversity refers toa library having members that are exposed to different processingconditions and may or may not possess different chemical properties as aresult of the different process history. Different processing conditionsinclude varying the ratios of compounds and reagents, time of reaction,reaction temperature, reaction pressure, rate of starting componentaddition to the reaction, residence time (or product removal rate),reaction atmosphere, mixing rate, or other conditions that those ofskill in the art will recognize It is through the creation of librarieshaving diversity and the screening of such libraries for a property orcompound of interest that a complete combinatorial research anddevelopment program may be undertaken for olefin polymerizationreactions.

An “array” refers to a spatial orientation of the members of one or morelibraries to facilitate combination with other libraries or librarymembers.

In particular, this invention provides the method and apparatus for thesynthesis of libraries of transition metal complexes, cocatalysttherefor, and polymerization modifiers or arrays of any two or more ofthe foregoing, by a variety of routes for evaluation as catalystcompositions. Preferably, the invention relates to a technique for theidentification of polymerization modifiers that optimize or improve oneor more aspects of an olefin polymerization process or product.Additional components for the catalyst composition may be ordered aslibraries or included as a constant or standardized reagent. Activationof these transition metal complexes into activated compositions byvaried techniques may be included as well, particularly when thecocatalyst or activator is one of the variables to be studied orscreened. After the transition metal complex, cocatalyst, and/orpolymerization modifier libraries are prepared, the invention providesfor forming arrays thereof and screening of one or more resultingproperties. Screening may be in, for example, a series of individualpolymerization reactors that provides detailed information aboutcatalytic activity under a variety of reaction options and conditions,including monomer and comonomer choice, solvent, pressure, temperature,stirring rate, volume, stoichiometric relationships, and order ofaddition of chemicals. Thus, one may choose to “combinatorialize” any ofthe polymerization reaction conditions for single or multiple librariesor for an array. By this is meant that individual members of the variouslibraries are combined and optionally subjected to one or more processsteps to ultimately form a catalyst composition which is tested for oneor more olefin polymerization properties, polymer properties or otherperformance properties. Optional steps in this addition polymerizationcombinatorial process may include a primary screen prior to screening inthe individual polymerization reactors. A primary screen may, forexample, comprise an optical screen that simply determines which membersof the catalyst library form a homogeneous solution. Another optionalstep is to further characterize the resultant polymers formed in thepolymerization reactor. Such further screening may employ a rapid liquidchromatography and/or light scattering system, or determination of thechemical, physical or mechanical properties of the resultant polymers.

The members of a precursor library, procatalyst library, catalystlibrary, arrays formed therefrom, or a product library are typicallystored or provided in a spatially addressable format, meaning that eachcompound or mixture is separated from the others, generally in a liquidform such as a solution or slurry, and retained in a sealed vial. Due tothe corrosive nature of many of the components, reagents or solventsemployed in forming the various libraries, the individual vials, allreaction vessels, and even the entire combinatorial apparatus arepreferably retained under inert atmospheric conditions. Allmanipulations are performed under inert atmospheric or high vacuumconditions.

One option for the creation of the procatalyst library may include thegeneration of stock solutions of the transition metal complex,cocatalyst and/or polymerization modifier libraries, so that each memberof the catalyst composition library is made of the same parent librarymembers by means of different reactions or under different reactionconditions or by combination with different reactions and reactionconditions. In a preferred embodiment, the transition metal complexlibrary, cocatalyst library, and polymerization modifier library areprovided in a liquid form, for example with each compound stored in aseparate vessel, preferably in dilute form or as a slurry (for example,where a solid catalyst support is included) in a liquid such as ahydrocarbon, halocarbon or halohydrocarbon. Preferably, the compounds ormixtures comprising the parent library are stored in vials having aseptum or other sealing mechanism that can be penetrated by a needlethat may be on a robotic arm of known liquid handling robots or they areproduced by combination of such components prior to or at the same timeas the polymerization of interest.

Various catalyst compositions may be formed from combinations of theother libraries or standards to thereby form an array. In a preferredembodiment, at least one member from the catalyst precursor library iscombined with at least one cocatalyst and one polymerization modifier.Alternatively, a statistical approach may be used to randomize thevarious components to be tested, optionally including repetition of oneor more array members for purposes of determining random or non-randomvariation. Highly desirably the libraries are combined and reactionconditions varied so as to form at least 8, preferably at least 24, morepreferably at least 32, and most preferably at least 48 catalyst librarymembers or polymerization process members of the resulting array.

In some embodiments, the various compounds, especially the PMcomponents, may be combined without determination of the product of suchcombination, or if, in fact, a product forms at all. The metal complex,cocatalyst, and polymerization modifier may be added to the reactionvessel at the same time or sequentially. They may be added before, alongwith or subsequent to addition of any additional reactants or themonomers used in the reaction of interest. Alternatively, some or all ofthe compounds may be prereacted or combined and recovered or purifiedprior to use in a subsequent process. In all of the foregoing processes,the result of any single or multiple combination need not be determined.

The product library (catalyst composition or polymer) may have differentmembers resulting from combinatorializing the process variables in thereaction of interest. Process variables that may be combinatorializedinclude the types, amounts, and ratios of starting components, time forreaction, reaction temperature, reaction pressure, rate and/or method ofstarting component addition to the reaction (or reactor), residence time(that is the rate and/or method of product removal from the reaction orreactor), reaction stir rate and/or method, reaction kill rate and/ormethod, reaction atmosphere, and other conditions that those of skill inthe art will recognize.

Those of skill in the art will appreciate the vast number of differentpossible combinations of precursors, modifiers, activators, or otherstarting components that may be combined together to form the catalystcomposition libraries. In addition, this combination methodology may becombined with combinations of various reaction conditions, includingdifferent starting component ratios, different temperatures, solvents,pressures, mixing rates, times, order of addition of chemicals oratmospheres to form extensive product libraries.

In the methodology of this invention, a library is screened for aproperty or compound of interest. The screening takes place as thereaction of interest is being performed, that is, in real time orsubsequent to the reaction. As used herein, “screening” refers totesting a library for a desired property by measurement of one or moreproduct or process variables, preferably one or more process variablesunder addition polymerization conditions. A screen of one or moreprocess variables may be combined with the evaluation of productproperties of interest, if desired. For example, polymerizationreactions performed in a polymerization reactor, especially a solutionpolymerization reactor, can be evaluated by monomer consumption,temperature evolution, and/or pressure-, viscosity-, particle size-, orcolor-change, and these results individually or collectively correlatedwith one or more polymer properties. Examples of suitable polymerproperties that may be so correlated with the on-line process datainclude molecular weight, molecular weight distribution, comonomercontent, crystalline melting point, melt index, flow index, or othermelt flow properties, tacticity, solubility, density, and so forth.

Each of the various libraries may be stored in a liquid or solid stateand retrieved from storage for combining, daughtering, running in thereaction of interest, screening, or combinations thereof. Libraries arepreferably stored in a storage rack that holds the libraries separatelyfrom each other. Libraries may be retrieved from storage either manuallyor automatically, using known automated robots. Specific robots usefulfor retrieving such stored libraries include systems such as thosemarketed by Aurora Biosciences or other known robotic vendors. If thelibraries are stored in the solid phase, the members typically requiredissolution or slurrying, which may be performed at a dissolution orslurrying station, or if sufficient volume is provided for librarystorage, in the vessel or chamber holding the sample. A dilution stationis a location where the library members are dissolved in a suitablesolvent or where more concentrated solutions of the library members arediluted before use in either the reaction of interest or in a screen.

Each transition metal complex, cocatalyst, polymerization modifier, orcatalyst composition libraries may be converted into one or moredaughter libraries through formation of arrays. A daughter library iscreated from the parent library by taking one or more aliquots from oneor more members in the parent library, and optionally treated todiffering conditions than the parent library or otherwise converted, toform a second library. A limited number of members of the parent librarymay be daughtered in this manner, or all the members may be daughteredat least once to create a daughter library. Thus, a daughter library maybe smaller, the same size as, or larger than the parent library in termsof both the number of members and the sample size. Daughtering isperformed in order to provide multiple libraries for multiple reactionsof interest or multiple screens without having to recreate the parentlibrary.

As used herein a “station” is a location in the apparatus that performsone or more functions to the members of a library. The functions may becombining the starting components, creating a product library via areaction, screening, purifying, separating, or performing any of theother functions discussed above. Thus, the station may comprise a liquidhandling robot with pumps and computers (as known in the art) todispense, dissolve, mix and/or move liquids from one container toanother.

The station may comprise any of the reactors discussed above, and may beremotely located from the remainder of the apparatus, such as in aninert atmosphere glove box, if desired. A station may also performmultiple functions, optionally separated by cleaning, reconditioning orresetting of the equipment, if desired.

Optionally a filtering station is provided. The filtering station isuseful to separate solid phase agents or products from liquid productsor compositions. For example, if solid-phase by-products form, such astation will allow for separation of any liquid phase components in afiltering step. Alternatively, if soluble reaction products are desiredfor further use herein, filtration may be employed to remove undesiredby-products. Desirably, the filtering station can be used multiple timesby restoring original process conditions after each filtration.

A filtering station provides for ease in the synthesis of the metalcomplex, cocatalyst and polymerization modifier libraries. The variouscomponents of the catalyst composition may be provided in the solid orliquid phase in a single reactor, while various reagents, solvents andpolymerization modifiers are combined and excess reagents or by-productsremoved. This technique generally allows for the use of an excess of anyreagent or solvent, ease of purification or work-up, and automation ofthe process.

Suitable techniques for screening useful herein include infrared (IR)thermography or Fourier Transform Infrared (FTIR) spectroscopy orvisible light or other optical viewing as disclosed in WO 98/15815 or WO98/15805. Using an optical technique typically entails inserting thestarting materials (that is the catalyst composition library member withreactants and/or monomer) in an array format into a chamber (forexample, a vacuum chamber or a chamber pressurized with reactant monomeror a chamber pressurized with an inert gas). The reaction of interest isperformed in parallel in the chamber using a plate having multiple wellsfor the catalyst members or starting materials for the product members(such as a microtiter plate, for example) or individually. The chamberhas a window that is invisible to the optical camera (for example by useof a calcium fluoride or sapphire crystal for an IR camera). As thereaction of interest is carried out, the reaction is monitored. Forexample, an IR camera or thermocouple may record heat released by thereaction. A preferred method for monitoring a process condition is tomeasure consumption of one or more monomers, typically by measuring flowor pressure loss of one or more monomers in an otherwise sealed reactoror the pressure decrease with time within a sealed reactor operatingunder polymerization conditions.

Because of the wide applicability of this invention to a broad varietyof polymerization conditions, a combinatorial approach can be used toidentify optimum catalyst compositions for use in different additionpolymerization reactions. An advantage to the present combinatorialapproach is that the choice of metal complex, cocatalyst, andpolymerization modifier can be tailored to specific polymerizationconditions.

The scale of the polymerizations employed in the present screeningoperations preferably employs transition metal complexes, cocatalystsand polymerization modifiers in an amount from 0.01 μg to 1.0 g, morepreferably between one 0.1 μg to 0.1 g, although the scale can bemodified as desired depending on the equipment used. Those of skill inthe art can readily determine appropriate sets of reactions and reactionconditions (including addition of one or more impurities) to generateand/or evaluate the libraries of interest.

The members of the various libraries can be laid out in a logical or arandom fashion in multi-tube arrays or multi-well plates, preferably inthe form an array. Preferably, the liquids are dilute solutions orslurries of the compound or mixture of interest. In a preferredembodiment, an A×B array is prepared, with various combinations of metalcomplex, cocatalyst and polymerization modifier of interest. However, itis also possible to evaluate a single transition metal complex orcocatalyst with a plurality of polymerization modifiers, monomers,impurities, or other additives, optionally at different polymerizationtemperatures, concentrations, pressures, monomers, or other reactionconditions, and then repeat the process as desired with a plurality ofdifferent subject compounds.

The performance of the particular combination of library member,reagent, or process condition under the reaction conditions of interestis measured and correlated to the specific combination tested.Adjustments to the data to compensate for non-standard conditions,systematic variation, or other variables can be applied. In addition,statistical analyses may be performed to manipulate the raw data anddetermine the presence of data variation. The array can be ordered insuch a fashion as to expedite synthesis and/or evaluation, to maximizethe informational content obtained from the testing, or to facilitatethe rapid evaluation of such data, if desired. Methods for organizinglibraries of compounds are well known to those of skill in the art, andare described, for example, in U.S. Pat. No. 5,712,171. Such methods canbe readily adapted for use with the compounds and process parametersdescribed herein.

By screening multiple synthetic variations of a transition metalcomplex, cocatalyst, polymerization modifier, or resulting catalystcomposition, the selection of the optimal candidate may be rapidlydetermined. The desired physical and chemical properties for the variouslibrary- or daughter library-members can be rapidly optimized, anddirectly correlated with the chemical or physical changes within aparticular array or sub-array.

The polymerizations using the various members in the libraries generallyinvolve contacting appropriate mixtures thereof under polymerizationconditions in the tubes or wells in a multi-tube rack or multi-wellplate, on a titer plate, or in a matrix of an inert support material,and allowing the addition polymerization reaction to take place whilemonitoring one or more process variables, especially heat evolution ormonomer consumption. Because of the ease and accuracy of monitoringgaseous flow, ethylene consumption in the polymerization of interest,optionally correlated with heat evolution, is the most desired processvariable for screening herein. Secondary screening of polymerproperties, especially tacticity, molecular weight, or comonomercomposition are further optionally correlated with the process dataaccording to the present invention.

Robotic arms and multi-pipet devices are commonly used to addappropriate reagents to the appropriate polymerization reactors, such asthe tubes in multi-tube racks, or wells in multi-well plates.Alternatively, but less desirably, a common polymerization reactor canbe employed sequentially to conduct the subject polymerizations. Thetubes are desirably covered with a rubber septum or similar cover toavoid contamination, and the reagents added via injection through aneedle inserted through the cover. Suitable process equipment for theforegoing operations has been previously disclosed in U.S. Pat. Nos.6,030,917,6,248,540 and EP-A-978,499.

In one embodiment, the polymerizations are carried out via computercontrol. The identity of each of the compounds of the library can bestored in a computer in a “memory map” or other means for correlatingthe data regarding the polymerizations. Alternatively, the chemistry canbe performed manually, preferably in multi-tube racks or multi-wellplates, and the resulting information stored, for example on a computer,if desired.

Any type of multi-well plate or multi-tube array commonly used incombinatorial chemistry can be used. Preferably, the number of wells ortubes is in excess of 30, and there is a tube in at least 60 percent ofthe positions in each multi-tube array. The shape of the rack is notimportant, but preferably, the rack is square or rectangular. The tubescan be made, for example, from plastic, glass, or an inert metal such asstainless steel. Because of the relatively high temperatures employed inthe polymerization screens, desirably in excess of 100° C. morepreferably in excess of 110° C., preferably glass- or metal-, and mostpreferably stainless steel-, reactors are employed.

Any type of liquid handler that can add reagents to, or remove reagentsfrom, the wells and/or tubes of the array can be used. Many suchhandlers involve the use of robotic arms and robotic devices. Suitabledevices are well known to those of skill in the art of combinatorialchemistry. The individual cells are also desirably equipped with oraccessible by a filter means through which liquid reagents, products orby-products can be removed, leaving solid products or reagents in thecell. Isolation of polymer products can be accomplished usingcommercially available centrifugal devolatilizers or evaporators, andneedn't be part of the automated procedures of the process.

Any device that can take samples from the polymerization reactor(s) andanalyze the contents can be used for product screening. Examples includechromatographic devices, such as an analytical or preparative scale highperformance liquid chromatography (HPLC), GC or column chromatography.For analysis of polymer properties simple solution viscosity, meltviscosity, ¹H NMR, ¹³C NMR, FTIR, xylene solubility (XS) studies, orother common analytical techniques may be employed for determination ofpolymer properties.

Preferably, in those embodiments in which a chromatographic column(HPLC, GC or column chromatography) is used, the device has the abilityto identify when the compound of interest is eluting from the column.Various means have commonly been used to identify when compounds ofinterest are eluting from a column, including ultraviolet (UV), infrared(IR), thin layer chromatography (TLC), gas chromatography-massspectrometry (GC-MS), flame ionization detector (FID), nuclear magneticresonance (NMR), and evaporative light scattering detector (ELSD). Anyof these means, and others known to those of skill in the art, can beused, alone or in combination.

The invention preferably includes a computer system capable of storinginformation regarding the identity of the compounds and mixtures in thelibraries and the product streams obtained from the polymerizations.Software for managing the data is stored on the computer. Relationaldatabase software can be used to correlate the identity of the compoundsemployed in each polymerization and the results. Numerous commerciallyavailable relational database software programs for this purpose areavailable and known to the skilled artisan. Although relational databasesoftware is a preferred type of software for managing the data obtainedduring the processes described herein, any software that is able tocreate a “memory map” of the test compounds and correlate thatinformation with the information obtained from the polymerizations canbe used.

The present invention is beneficially employed with respect to thepolymerization of one or more addition polymerizable monomers. Preferredaddition polymerizable monomers include ethylenically unsaturatedmonomers, acetylenic compounds, conjugated or non-conjugated dienes, andpolyenes. Preferred monomers include olefins, particularly α-olefinshaving from 2 to 20,000, preferably from 2 to 20, more preferably from 2to 8 carbon atoms, combinations of two or more of such alpha-olefins,and combinations of one or more such α-olefins with one or morediolefins. Particularly suitable α-olefins include, ethylene, propylene,1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, and combinations thereof. Other preferred additionpolymerizable monomers include styrene, halo- or alkyl substitutedstyrenes, tetrafluoroethylene, vinylcyclobutene, 1,4-hexadiene,dicyclopentadiene, ethylidene norbornene, and 1,7-octadiene.

The following specific embodiments of the invention are especiallydesirable and hereby delineated in order to provide specific disclosurefor the appended claims:

1. A method for identifying a catalyst composition for use in thehomogeneous addition polymerization of one or more additionpolymerizable monomers, said catalyst composition comprising a catalystprecursor compound of a metal of Groups 3-11 of the Periodic Table ofthe Elements, a cocatalyst and a polymerization modifier capable ofimproving one or more polymer or process properties, said methodcomprising:

A) providing at least one library comprising a plurality of catalystprecursor compounds i) comprising a metal of Groups 3-11 of the PeriodicTable of the Elements; at least one cocatalyst ii) capable of convertinga catalyst precursor compound into an active polymerization catalyst;and at least one compound iii) to be evaluated as a polymerizationmodifier;

B) sequentially converting a multiplicity of the catalyst precursorcompounds i) into compositions to be tested for polymerizationproperties by reaction thereof with one or more cocatalysts ii) and oneor more polymerization modifiers iii);

C) contacting the resulting composition of step B) or a portion thereofwith one or more addition polymerizable monomers under olefin additionpolymerization conditions in a polymerization reactor,

D) measuring at least one process or product variable of interest, and

E) selecting the catalyst composition of interest by reference to saidat least one process or product variable;

characterized in that the polymerization modifier iii) is prepared priorto use by reaction between two or more starting reagents.

2. A method for identifying a catalyst composition for use in thehomogeneous addition polymerization of one or more additionpolymerizable monomers, said catalyst composition comprising a catalystprecursor compound of a metal of Groups 3-11 of the Periodic Table ofthe Elements, a cocatalyst and a polymerization modifier capable ofimproving one or more polymer or process properties, said methodcomprising:

A) providing at least one catalyst precursor compound i) comprising ametal of Groups 3-11 of the Periodic Table of the Elements; at least onelibrary comprising a plurality of candidate cocatalysts ii) to beevaluated for converting catalyst precursor compound i) into an activepolymerization catalyst; and at least one compound iii) to be evaluatedas a polymerization modifier;

B) sequentially utilizing a multiplicity of the cocatalyst compounds II)to prepare compositions to be tested for polymerization properties byreaction thereof with one or more catalysts i) and one or morepolymerization modifiers iii);

C) contacting the resulting composition or a portion thereof with one ormore addition polymerizable monomers under olefin additionpolymerization conditions in a polymerization reactor,

D) measuring at least one process or product variable of interest, and

E) selecting the catalyst composition of interest by reference to saidat least one process or product variable;

characterized in that the polymerization modifier iii) is prepared priorto use by reaction between two or more starting reagents.

3. A method for identifying a catalyst composition for use in thehomogeneous addition polymerization of one or more additionpolymerizable monomers, said catalyst composition comprising a catalystprecursor compound of a metal of Groups 3-11 of the Periodic Table ofthe Elements, a cocatalyst and a polymerization modifier capable ofimproving one or more polymer or process properties, said methodcomprising:

A) providing at least one catalyst precursor compound i) comprising ametal of Groups 3-11 of the Periodic Table of the Elements; at least onecocatalyst ii) capable of converting catalyst precursor compound i) intoan active polymerization catalyst; and at least one library comprising aplurality of candidate compounds iii) to be evaluated as polymerizationmodifiers;

B) sequentially utilizing a multiplicity of the candidate polymerizationmodifier compounds iii) to prepare compositions to be tested forpolymerization properties by reaction thereof with one or more catalystsi) and one or more cocatalysts ii);

C) contacting the resulting composition or a portion thereof with one ormore addition polymerizable monomers under olefin additionpolymerization conditions in a polymerization reactor,

D) measuring at least one process or product variable of interest, and

E) selecting the catalyst composition of interest by reference to saidat least one process or product variable;

characterized in that the polymerization modifiers iii) are preparedprior to use by reaction between two or more starting reagents.

4. The method of any one of embodiments 1-3, wherein the polymerizationmodifier is prepared by reaction of one or more metal compounds of theformula: [M⁴A¹ _(x′)G_(y′)]_(z′), wherein:

M⁴ is a metal of Groups 2-13, Ge, Sn, or Bi;

A¹ is independently an anionic or polyanionic ligand;

x′ is a number greater than zero and less than or equal to 6;

G is a neutral Lewis base, optionally bound to A¹;

y′ is a number from 0-4;

z′ is a number from 1 to 10;

with one or more compounds of the formula: [(H-J¹)_(z″)A²]_(z′″),wherein:

J¹ is NA³, PA³, S, or O,

z″ is 1 or 2,

A² is C₁₋₂₀ hydrocarbyl or inertly substituted hydrocarbyl, or apolyvalent derivative thereof,

A³ is hydrogen, C₁₋₂₀ hydrocarbyl or inertly substituted hydrocarbyl, ora covalent bond (when A² is a divalent ligand group and z″ is one); and

z′″ is a number from 1 to 10.

5. The method of embodiment 4 wherein the polymerization modifier isprepared in solution and used without isolation or purification.

6. The method of embodiment 5 wherein the polymerization modifier isprepared by contacting hydrocarbon solutions of the starting reagents.

7. The method of embodiment 6 wherein step C) comprises combining thepolymerization modifier solution, monomer(s), Group 3-11 metal complex,and cocatalyst in any order or by forming any subcombination thereof.

8. The method of embodiment 4, wherein the cocatalyst comprises analumoxane, a tri(fluoroaryl)borane, or an ammonium salt of atetra(fluorophenyl)borate.

9. The method of embodiment 8, wherein ethylene, propylene, acombination of ethylene and propylene, or a combination of any of theforegoing with 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene,styrene, or ethylidenenorbornene is copolymerized.

10. The method of embodiment 9 wherein the catalyst comprises(1H-cyclopenta[l]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitaniumdimethyl, the cocatalyst comprises a trialkylammonium salt oftetrakis(pentafluorophenyl)borate, and a mixture of ethylene and styreneis copolymerized.

11. The method of embodiment 8, wherein the cocatalyst comprises amixture of methyldi(C₁₄₋₁₈ alkyl)ammoniumtetrakis(pentafluorophenyl)borate salts.

12. The method of embodiment 4, wherein the catalyst composition ofinterest is selected by reference to at least two variables selectedfrom process variables and product variables.

13. The method of embodiment 12, wherein the process variables are highcatalyst efficiency, monomer consumption, improved catalyst efficiencyat elevated polymerization temperature, and steady or increasingproductivity with increasing molar ratio of polymerization modifier totransition metal compound; and the product variable is reduced formationof high crystalline polymer fraction, or increased comonomerincorporation in a copolymer of ethylene and at least onecopolymerizable comonomer.

14. The method of embodiment 4, wherein all of the process steps areconducted in the same reactor vessel by means of computer controlled,robotic processing and the screening results are stored in at least onememory device.

15. The method of embodiment 14, wherein the library is used to form theA axis of an A×B array and a second selection of compositions or processconditions is used to form the B axis of said A×B array and relationaldatabase software is used to select the property of interest from amongthe set of binary pairs of said A×B array.

16. The method of embodiment 4 wherein the process variable that ismeasured is the quantity of at least one monomer consumed during thepolymerization.

17. The method of embodiment 1 wherein in step d) the property ofinterest is calculated conversion after 300 seconds based on thefollowing polymerization model:˜C*_(r)+M→˜C*_(r+1) k_(p) gaseous monomer propagation˜C*_(r)→DC k_(d) active site deactivationwhere:

˜C*_(r) is a growing chain with chain length r

M is the monomer

DC is dead polymer chain

k_(p) is the gaseous monomer propagation rate constant, and

k_(d) is the active site deactivation rate constant;

calculated as total gaseous monomer uptake versus time (t in seconds)according to the following equation:

$\begin{matrix}{{uptake} = \frac{k_{p} \cdot {{\lbrack M\rbrack_{liquid}\lbrack C\rbrack}_{0}\left\lbrack {1 - {\exp\left( {{- k_{d}} \cdot t} \right)}} \right\rbrack}}{k_{d}}} & {{Eq}\mspace{14mu} 1}\end{matrix}$

as determined according to the Levenberg-Marquart non-linear regressionmethod, where

[M]_(liquid) is the gaseous monomer concentration in the liquid phase,and

[C]₀ is the initial concentration of the catalyst at t=0.

18. The method of embodiment 17 wherein the 300 second monomer uptake isgreater than the corresponding value using triisobutylaluminum modifiedmethylalumoxane (MMAO) instead of the polymerization modifier at anMMAO:Ti molar ratio of 5:1.

19. A process for the polymerization of an olefin by contacting apolymerizable mixture comprising at least one olefin monomer and styreneunder polymerization conditions with a catalyst composition comprising atransition metal complex, a cocatalyst and a polymerization modifier,characterized in that the polymerization modifier is selected from thegroup consisting of ethylaluminum bis(N,N-diphenylamide) anddi(2,7-dimethyl-6-octene-1-yl)aluminum N,N-diphenylamide.

20. A process according to embodiment 19 wherein the metal complex is aGroup 4 metal complex and the cocatalyst is a Lewis acid or atrihydrocarbylammonium salt of a noncoordinating compatible anion.

21. A process for the copolymerization of ethylene and styrene to form apseudo-random copolymer by contacting a mixture comprising ethylene andstyrene under polymerization conditions with a catalyst compositioncomprising a metal complex, a cocatalyst and a polymerization modifier,characterized in that,

the metal complex comprises(1H-cyclopenta[l]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitaniumdimethyl;

the cocatalyst comprises tris(pentafluorophenyl)boron or atrialkylammonium salt of tetrakis(pentafluorophenyl)borate; and

the polymerization modifier is selected from the group consisting ofethylaluminum bis(N,N-diphenylamide) anddi(2,7-dimethyl-6-octene-1-yl)aluminum N,N-diphenylamide.

22. A process for the copolymerization of ethylene and 1-octene to forma copolymer by contacting a mixture comprising ethylene and 1-octeneunder polymerization conditions with a catalyst composition comprising ametal complex, a cocatalyst and a polymerization modifier, characterizedin that,

the metal complex comprises a 3-amino-substituted inden-1-yl complex oftitanium;

the cocatalyst comprises tris(pentafluorophenyl)boron or atrialkylammonium salt of tetrakis(pentafluorophenyl)borate; and

the polymerization modifier comprises a compound selected from the groupconsisting of: the 1:1 molar reaction product of t-butanol withtrioctylaluminum; the 1:1 molar reaction products of 2,6-diphenylphenol,2,6-di(t-butyl)-4-methylphenol, phenol, andt-butyldi(methyl)hydroxysilane with triisobutylaluminum; the 2:1 molarreaction products of di(n-pentyl)amine with triisobutylaluminum; the 2:1molar reaction product of 2,6-diphenylphenol, andt-butyldi(methyl)hydroxysilane with triethylaluminum; the 1:1 molarreaction products of 2,6-diphenylphenol, 2,6-di(t-butyl)-4-methylphenol,phenol, t-butanol, 1-dodecanol, t-butyldi(methyl)hydroxysilane, andp-methoxyphenol with trioctylaluminum; and the 2:1 molar reactionproducts of 2,6-diphenylphenol, 2,6-di(t-butyl)-4-methylphenol andt-butyldi(methyl)hydroxysilane with tri(octyl)aluminum.

23. The process of embodiment 22 wherein the metal complex comprises(N-1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-(tetrahydro-1H-pyrrol-1-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,3-pentadiene or(N-1,1-dimethylethyl)-1,1-(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-dimethyltitanium and the polymerization modifier comprises(t-butyldimethylsiloxy)diisobutylaluminum orbis(t-butyldimethylsiloxy)octylaluminum.

24. A process for the copolymerization of ethylene and 1-octene to forma copolymer by contacting a mixture comprising ethylene and 1-octeneunder polymerization conditions with a catalyst composition comprising ametal complex, a cocatalyst and a polymerization modifier, characterizedin that,

the metal complex comprises an s-indacenyl silanaminato complex oftitanium;

the cocatalyst comprises tris(pentafluorophenyl)boron or atrialkylammonium salt of tetrakis(pentafluorophenyl)borate; and

the polymerization modifier comprises a compound selected from the groupconsisting of the 1:1 molar reaction products of phenylnaphthylamine,triethylhydroxysilane, n-butanol, or benzoic acid withtriisobutylaluminum; 2,6-diphenylphenol, 4-methyl-2,6-di(t-butyl)phenol,triethylhydroxysilane, n-butanol or 2-hydroxymethylfuran withtrioctylaluminum; and phenol or 2-(hydroxymethylipyridine withdibutylmagnesium.

25. The process of embodiment 24 wherein the metal complex comprises[N-(1,1-dimethylethyl)-1,1-dimethyl-[1,2,3,3a,8a-η)-1,5,6,7-tetrahydro-2-methyl-s-indacen-1-yl]silanaminto(2-)-N]titanium(II) 1,3-pentadiene and the polymerization modifier comprises(phenyl(naphthyl)amino)diisobutylaluminum,(triethylsiloxy)diisobutylaluminum, (n-butoxy)-diisobutylaluminum,diisobutylaluminum benzoate; 2,6-diphenylphenoxy(dioctyl)aluminum,4-methyl-2,6-dit-butylphenoxyldioctylaluminum,(triethylsiloxy)dioctylaluminum, (n-butoxy)-dioctylaluminum,(2-furanylmethoxy)dioctylaluminum; phenoxy-n-butylmagnesium, or(2-pyridinylmethoxy)-n-butylmagnesium.

26. A process for the copolymerization of ethylene and propylene to forma copolymer by contacting a mixture comprising ethylene and propyleneunder polymerization conditions with a catalyst composition comprising ametal complex, a cocatalyst, and a polymerization modifier,characterized in that,

the metal complex comprises a complex of hafnium and a pyridylamine;

the cocatalyst comprises tris(pentafluorophenyl)boron or atrialkylammonium salt of tetrakis(pentafluorophenyl)borate; and

the polymerization modifier comprises the reaction product of atri(C₂₋₂₀alkyl)aluminum with bis(trimethylsilyl)amine, 1-octanol,1-dodecanol, phenol, 4-methyl-2,6-di(t-butyl)phenol, ort-butyldimethylsiloxane.

27. The process of embodiment 26 wherein the metal complex comprises2-[N-(2,6-diisopropylphenylamido)-o-isopropylphenylmethyl]-6-(2-η-1-naphthyl)-pyridylhafnium(IV) dimethyl, the cocatalyst comprises a mixture ofmethyldi(C₁₄₋₁₈) long chain alkyl ammoniumtetrakis(pentafluorophenyl)borate salts, and the polymerization modifiercomprises (dodecyloxy)dioctylaluminum,(bis(trimethylsilyl)amino)dioctylaluminum, phenoxydioctylaluminum,(4-methyl-2,6-di(t-butyl)phenoxy)dioctylaluminum,(t-butyldimethylsiloxy)dioctylaluminum,bis(trimethylsilyl)aminodiethylaluminum, orbis(t-butyldimethylsiloxy)isopropylaluminum.

EXAMPLES

It is understood that the present invention is operable in the absenceof any component which has not been specifically disclosed. Thefollowing examples are provided in order to further illustrate theinvention and are not to be construed as limiting. Unless stated to thecontrary, all parts and percentages are expressed on a weight basis. Theterm “overnight”, if used, refers to a time of approximately 16-18hours, “room temperature”, if used, refers to a temperature of about20-25° C., and “mixed alkanes” refers to a mixture of hydrogenatedpropylene oligomers, mostly C₆-C₁₂ isoalkanes, available commerciallyunder the trademark Isopar E™ from ExxonMobil Chemicals, Inc.

Catalyst Composition Library Preparation:

A library of compounds for testing as polymerization modifiers isprepared by robotic synthesis using a Chemspeed™ synthesizer, model ASW2000 (available from Chemspeed, Inc.) equipped with 16×13 mL reactorsets. Typically, five sets of 16×13 mL reactors with reflux condensors,for a total of 80 reactors, are installed on the robotics deck. Thereagents for each library are prepared in the drybox and transferred tothe robotics deck. The vials used in the preparation and containment ofthese reagents are dried in an oven at 150° C. for at least 4 hoursprior to use. All reactions are performed under inert atmosphere.

Using software control, the reactors are heated to 110° C. for at leastfour hours while under vacuum, followed by 60 minutes at 110° C. whileunder an argon purge to dry the reactors. The reactors are then cooledto ambient temperature. The cannula and sample loops are primed with drynitrogen, and then the sample loop is passivated by aspirating thevolume of the sample loop (usually 10000 or 25000 uL) with 1 M AlEt₃ intoluene. This solution is then disposed of at the rinse station and thecannula and sample loop are rinsed with fresh toluene. Using the liquidhandler, the 80 reactors are then charged with the first reagent(trialkylaluminum) solutions. The vortexer is started (800 rpm) and thejacket temperature of the reactors is set at 25° C. with the refluxcondensors set to 5° C. The second reagent solutions (amines oralcohols) are then charged to the reactors at an addition rate of 5mL/min After all of the additions are completed, the reactors are closedunder argon and heated to 100° C. for five hours, then cooled to 50° C.before vortexing is stopped.

The reagent tray is then changed to accommodate 20 mL sample vials.Using the liquid handler, the contents of each reactor are transferredto a serum capped 20 mL vial. The sample is then diluted to give anapproximately 0.1 M solution of the desired polymerization modifier.After transferring the products, the sample is capped under the nitrogenatmosphere of the synthesizer purge box, and then transferred to adrybox for storage prior to use.

Either one or two equivalents of second reagent (B) are reacted with thefirst reagent (A) in a hydrocarbon diluent, typically hexane or heptane,to generate a library of compounds for further screening. The reagentsare initially contacted at 20-25° C. followed by heating at reflux forseveral hours. The pairs of reagents tested are identified in Table 1.The products are the corresponding stoichiometric reaction products,excepting for (B3)₃A2₂ (a product with 3 B groups to 2 A groups) whichresulted upon combining two equivalents of B3 with one equivalent of A2.

TABLE 1

Al(Et)₃ A2 Al(Me)₃ A3

1:1 2:1 1:1 2:1 1:1 2:1 1:1 2:1 1:1 2:1

B1A1 B1₂A1 B1A2 B1₂A2 B1A3 B1₂A3 B1A4 B1₂A4 B1A5 B1₂A5

B2A1 B2₂A1 B2A2 B2₂A2 B2A3 B2₂A3 B2A4 B2₂A4 B2A5 B2₂A5 Ph₂NH, B3A1 B3₂A1B3A2 B3₂A2₂ B3A3 B3₂A3 B3A4 B3₂A4 B3A5 B3₂A5 B3

B4A1 B4₂A1 B4A2 B4₂A2 B4A3 B4₂A3 B4A4 B4₂A4 B4A5 B4₂A5

B5A1 B5₂A1 B5A2 B5₂A2 B5A3 B5₂A3 B5A4 B5₂A4 B5A5 B5₂A5 (benzyl)₂NH B6A1B6₂A1 B6A2 B6₂A2 B6A3 B6₂A3 B6A4 B6₂A4 B6A5 B6₂A5 B6 (i-Pr)₂NH B7A1B7₂A1 B7A2 B7₂A2 B7A3 B7₂A3 B7A4 B7₂A4 B7A5 B7₂A5 B7

B8A1 B8₂A1 B8A2 B8₂A2 B8A3 B8₂A3 B8A4 B8₂A4 B8A5 B8₂A5 (Me₃Si)₂NH B9A1B9₂A1 B9A2 B9₂A2 B9A3 B9₂A3 B9A4 B9₂A4 B9A5 B9₂A5 B9 Ph—OH, B10A1 B10₂A1B10A2 B10₂A2 B10A3 B10₂A3 B10A4 B10₂A4 B10A5 B10₂A5 B10 t-Bu—OH, B11A1B11₂A1 B11A2 B11₂A2 B11A3 B11₂A3 B11A4 B11₂A4 B11A5 B11₂A5 B11

B12A1 B12₂A1 B12A2 B12₂A2 B12A3 B12₂A3 B12A4 B12₂A4 B12A5 B12₂A51-dodecanol B13A1 B13₂A1 B13A2 B13₂A2 B13A3 B13₂A3 B13A4 B13₂A4 B13A5B13₂A5 B13 1-octadecanol B14A1 B14₂A1 B14A2 B14₂A2 B14A3 B14₂A3 B14A4B14₂A4 B14A5 B14₂A5 B14 (t-Bu)(Me)₂SiOH B15A1 B15₂A1 B15A2 B15₂A2 B15A3B15₂A3 B15A4 B15₂A4 B15A5 B15₂A5 B15 HN(n-C₅H₁₁)₂ B16A1 B16₂A1 B16A2B16₂A2 B16A3 B16₂A3 B16A4 B16₂A4 B16A5 B16₂A5 B16

B17A1 B17₂A1 B17A2 B17₂A2 B17A3 B17₂A3 B17A4 B17₂A4 B17A5 B17₂A5

B18A1 B18₂A1 B18A2 B18₂A2 B18A3 B18₂A3 B18A4 B18₂A4 B18A5 B18₂A5

B19A1 B19₂A1 B19A2 B19₂A2 B19A3 B19₂A3 B19A4 B19₂A4 B19A5 B19₂A5

B20A1 B20₂A1 B20A2 B20₂A2 B20A3 B20₂A3 B20A4 B20₂A4 B20A5 B20₂A5

B21A1 B21₂A1 B21A2 B21₂A2 B21A3 B21₂A3 B21A4 B21₂A4 B21A5 B21₂A5

B22A1 B22₂A1 B22A2 B22₂A2 B22A3 B22₂A3 B22A4 B22₂A4 B22A5 B22₂A5

B23A1 B23₂A1 B23A2 B23₂A2 B23A3 B23₂A3 B23A4 B23₂A4 B23A5 B23₂A5

Example 1

Evaluation of the foregoing compositions in the polymerization ofmixtures of ethylene and styrene is conducted in a 48 cell parallelpressure reactor (PPR) equipped with rapid gel permeation chromatography(HTGPC) for polymer molecular weight determination. Each cell is fittedwith a 16 mL glass insert for conducting the polymerization. The metalcomplex employed in the catalyst composition is(1H-cyclopenta[l]phenanthrene-2-yl)-dimethyl(t-butylamido)silane-titaniumdimethyl (C1), prepared according to the teachings of U.S. Pat. No.6,150,297 (100 nmole). The structure of C1 is disclosed in FIG. 1. Thecocatalyst is a mixture of methyldi(C₁₄₋₁₈) long chain alkyl ammoniumtetrakis(pentafluorophenyl)-borate salts (110 nmole). The candidatepolymerization modifiers (PM) are tested at PM:Ti molar ratios of 5, 15,50 and 200, polymerization temperatures of 120° C. and a pressure of 200psi (1.4 MPa). The amount of styrene present in each reactor is 611 μL(533 μmol). Reagent details are contained in Table 2.

TABLE 2 Concentration Reagent Quantity (Molar) Toluene Variabledepending on PM NA (solvent) quantity Ethylene  200 psig (1.4 MPa) 0.48M cocatalyst 0.011M  100 μL (110 nanomol) 1.71 × 10⁻⁵ M in toluenePolymerization Modifier (PM), 0.050M in toluene/hexane  5:1  10 μL (500nanomol) 7.75 × 10⁻⁵ M  15:1  30 μL (1,500 nanomol) 23.2 × 10⁻⁵ M  50:1 100 μL (5,000 nanomol) 77.5 × 10⁻⁵ M 200:1  400 μL (20,000 nanomol) 310× 10⁻⁵ M Styrene  611 μL (533 μmol) 0.827 M (comonomer) catalyst, 0.010Min  100 μL (100 nanomol) 1.55 × 10⁻⁵ M toluene 6450 μL total volume

The empty mass of each 16 mL glass insert is measured robotically.Toluene (variable) is measured into each reactor cell. The reactors arethen stirred (800 rpm) and heated to the run temperature, 120° C. Atthis time, all the reactors are saturated with ethylene and eachindividual reactor is charged with a premixture of cocatalyst andpolymerization modifier, followed by styrene. The polymerizationreaction is then initiated by the addition of catalyst while thetemperature is maintained at 120° C. and the pressure is maintained at200 psi (1.4 MPa). The reaction is allowed to proceed for 10 minuteswith ethylene provided on demand. After the run time, the reactor isquenched with 5 percent CO₂ in argon. After all the reactors arequenched, they are cooled and vented. Volatiles are removed in acentrifuge under vacuum overnight.

Polymerization results are evaluated on the basis of threerequirements 1) efficiency, 2) minimal high crystalline fractionformation, and 3) desirable profile of ethylene conversion as a functionof PM/Ti ratio. Polymerization modifiers meeting one or more of theforegoing criteria are identified in Table 3. Efficiency is measuredagainst a standard catalyst composition in which triisobutylaluminummodified methylalumoxane (MMAO-3A, available from Akzo-NobleCorporation) is used as the polymerization modifier (comparative).However, because of statistically suspect results for the minimum andmaximum PM contents (Al/Ti ratios of 5 and 200 respectively)efficiencies are screened based only on results obtained at Al/Ti ratiosof 15 and 50. Polymerization modifiers leading to equal or betterefficiencies than the comparative are preferred for use herein. In Table3, acceptable efficiency performances according to this standard areidentified by numeral 1.

High crystalline fraction (HCF) refers to an ethylene/styreneinterpolymer (ESI) having very low levels of styrene incorporation andcorrespondingly high crystallinity. It is also generally of lowersolubility in a solution polymerization process and is implicated inpoor reactor operability. The presence of such HCF polymer isidentifiable from a GPC plot of the polymer. The use of higherpolymerization temperatures can at least partially mitigate operabilityproblems associated with the presence of significant quantities of HCFin the polymer, however, its presence is generally undesired due to itsdetrimental effect on product properties as well. Accordingly, apolymerization modifier that results in minimal HCF formation isdesired. In Table 3, acceptable (non-detectable or minimal) HCFidentified in the GPC plot of the ESI is indicated by numeral 2.

Ethylene polymerization profile refers to a lack of maximum ethyleneconversion as a function of PM:Ti molar ratio, at least within ranges ofPM:Ti that are economically justifiable. The presence of such a maximum,especially if use of additional polymerization modifier causes rapidloss of catalyst efficiency (peaking profile) requiring the operator toconstantly adjust polymerization modifier content during polymerizationto avoid detrimental effect on polymerization activity. An efficiencyprofile that increases through the range of interest or reaches aplateau without significant loss of activity at higher ratios is mostdesired. In Table 3 acceptable conversion performance (plateau orrising) is identified by a numeral 3 with rising profiles noted. Onlythose second components tested that have at least one acceptable PM areidentified in Table 3.

TABLE 3 ESI Polymerization Results

Al(Et)₃ A2 Al(Me)₃ A3

1:1 2:1 1:1 2:1 1:1 2:1 1:1 2:1 1:1 2:1

B1A1 1, 3 B1A2 1, 2 B1₂A2 1 B1A4 1, 3 B1₂A4 1 B1A5 1, 3* B1₂A5 1, 3*

B2₂A3 1, 3 B2A4 1, 3. Ph₂NH, B3 B3₂A1 1, 3*

B3A4 1, 2, 3* (Me₃Si)₂NH B9A1 B9₂A3 B9₂A4 B9A5 B9 1 1 1 1, 3* Ph—OH,B10A5 B10 1, 3* t-Bu—OH, B11

B12A4 1, 3 B12A5 1, 3* 1-dodecanol B13A4 B13 1, 3 1-octadecanol B14A1B14₂A B14A4 B14₂A B14A5 B4 1, 3* 1, 3* 1 1, 3* 1, 3* *also exhibitsrising ethylene conversion as a function of Al/Ti ratio for entire rangetested

Polymerization modifiers meeting two and most preferably all three ofthe foregoing requirements for a given metal complex/cocatalystcombination are especially preferred. Only two polymerization modifiers,B3₃A2₂ and B3A4 (identified by bold type in table 3) of those testedsatisfy all three requirements of the foregoing screen. Thesepolymerization modifiers are identified as bis(N,N-diphenylamide)ethylaluminum and N,N-diphenylamidobis(2,7-dimethyl-6-octene-1-yl)aluminum.

Example 2

2a) The polymerization conditions of example 1 are substantiallyrepeated excepting 1-octene is employed in place of styrene and thepolymerization is conducted at 135° C. in mixed alkanes solvent toprepare an elastomeric ethylene/1-octene copolymer. A new polymerizationmodifier library is prepared utilizing only three aluminum containingreagents, triisobutyl aluminum (A1) triethyl aluminum (A2) and trioctylaluminum (A5).

The catalyst precursors employed in the catalyst compositions are3-amino-substituted inden-1-yl complexes of titanium,(N-1,1-dimethylethyl)-1,1-dimethyl-1-((1,2,3,3a,7a-η)-3-(tetrahydro-1H-pyrrol-1-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-titanium(II) 1,3-pentadiene (C2), prepared according to the teachings of U.S.Pat. No. 6,268,444, and(N-1,1-dimethylethyl)-1,1-(4-n-butylphenyl)-1-((1,2,3,3a,7a-η)-3-(1,3-dihydro-2H-isoindol-2-yl)-1H-inden-1-yl)silanaminato-(2-)-N-)-dimethyltitanium(C3), prepared according to the teachings of US 2003/0004286. Thestructures of C2 and C3 are disclosed in FIGS. 2 and 3. The cocatalystis a mixture of methyldi(C₁₄₋₁₈) long chain alkyl ammoniumtetrakis(pentafluorophenyl)borate salts. In addition a scavenger,triisopropylaluminum modified methylalumoxane (MMAO 3A, available fromAkzo-Noble Corporation) in a molar ratio based on Ti of 5:1 is employedin all formulations to react with impurities in the reaction mixture.

Range finding experiments are conducted to determine satisfactoryquantities of the various components at each temperature tested.Conditions are selected so that activity could be measured withoutexceeding equipment capacity. At 135° C., the ethylene pressure ischosen to be 194 psig (1.44 MPa), the amount of hexane solvent is 6.0μL, and the quantity of 1-octene employed is 819 μL. Additionalrepresentative conditions are provided in Table 4.

TABLE 4 Catalyst (C2) 85 μL 17 nmol Catalyst (C3) 100 μL  20 nmolCocatalyst 85 μL 20 nmol Cocatalyst 100 μL  24 nmol MMAO 85 μL 85 nmolMMAO  85 μL  100 nmol PM 85 μL 850 nmol  PM  85 μL 1000 nmol

In each experiment, the reactor cells are loaded with solvent, followedby 1-octene, MMAO and PM (for control runs PM is omitted). The cells arethen heated to 135° C. and pressurized with ethylene gas. The catalystand cocatalyst are premixed in a vial by the liquid handler and injectedinto the reactor to start the polymerization. Polymerization is stoppedafter 10 minutes reaction time or upon a decrease in pressure to 120psig (0.93 MPa) by quenching with carbon dioxide.

The PM choices are screened in duplicate within each PPR run. Thisallows for 22 candidate compounds per library along with four controlreactions that use MMAO in an Al: Ti molar ratio 5:1 and no PMcandidate. The PM:Ti molar ratio for all PM polymerizations is 50:1.Seven libraries for each catalyst are screened providing a total of 154polymerization modifiers tested. Polymerization results are evaluated onthe basis of activity compared to a standard catalyst composition inwhich no PM is present. The top 10 candidates for each catalyst andtheir relative catalyst activities are reported in Table 5.

TABLE 5 Ethylene/1-octene 135° C. Polymerization Results

Al(Et)₃ A2

1:1 2:1 1:1 2:1 1:1 2:1

C2 (1.42) C1 (1.81) C1 (1.81) C1 (1.81)

C2 (1.40) C1 (1.81) C2 (1.37)   C2 (1.42) Ph—OH, C2 (1.84) C2 (1.74) B10t-Bu—OH, C2 (1.70) B11 1-dodecanol C2 (1.74) B13 1-octadecanol B14(t-Bu)(Me)₂SiOH C1 (1.75) C1 (1.75) C1 (1.35) C1 (1.35) B15 C2 (1.44) C2(1.29) HN(n-C₅H₁₁)₂ C1 (1.35) B16

C1 (1.60)

At 135° C. with one or the other of the foregoing metal complexes thebest polymerization modifiers are: the 1:1 molar reaction product oft-butanol with trioctylaluminum, that is, dioctylt-butoxyaluminum; the1:1 molar reaction products of 2,6-diphenylphenol,2,6-di(t-butyl)-4-methylphenol, phenol, andt-butyldi(methyl)hydroxysilane with triisobutylaluminum; the 2:1 molarreaction products of di(n-pentyl)amine with triisobutylaluminum; the 2:1molar reaction product of 2,6-diphenylphenol, andt-butyldi(methyl)hydroxysilane with triethylaluminum; the 1:1 molarreaction products of 2,6-diphenylphenol, 2,6-di(t-butyl)-4-methylphenol,phenol, t-butanol, 1-dodecanol, t-butyldi(methyl)hydroxysilane, andp-methoxyphenol with trioctylaluminum, and the 2:1 molar reactionproducts of 2,6-diphenylphenol, 2,6-di(t-butyl)-4-methylphenol andt-butyldi(methyl)hydroxysilane with tri(octyl)aluminum. These reactionproducts comprise primarily the following compounds:(2,6-diphenylphenoxy)di(1-butyl)aluminum,(2,6-di(t-butyl)-4-methylphenoxy)di(1-butyl)aluminum,phenoxydi(1-butyl)aluminum,(t-butyldi(methyl)siloxy)di(1-butyl)aluminum,(di(n-pentyl)amino)di(1-butyl)aluminum,bis(di(2,6-phenyl)phenoxy)ethylaluminum,bis((t-butyl)dimethylsiloxy)ethylaluminum,(2,6-diphenylphenoxy)dioctylaluminum,(2,6-di(t-butyl)-4-methylphenoxy)dioctylaluminum,(phenoxy)dioctylaluminum, (t-butoxy)dioctyl aluminum,(n-dodecyloxy)dioctylaluminum,((t-butyl)di(methyl)siloxy)dioctylaluminum,(4-methoxyphenoxy)dioctylaluminum,bis((2,6-diphenyl)phenoxy)octylaluminum,bis(2,6-di(t-butyl)-4-methylphenoxy)octylaluminum, andbis(t-butyldi(methyl)siloxy)octylaluminum. Three of the foregoing PM'sgave improved activity with both metal complexes, namely,(t-butyldi(methyl)siloxy)diisobutylaluminum,(2,6-di(t-butyl)-4-methylphenoxy)dioctylaluminum andbis(t-butyldi(methyl)siloxy)octylaluminum.

2b) Next, the 22 best PM candidates at 135° C. are retested forethylene/1-octene copolymerization properties with both metal complexesat 160° C. In this series of experiments, the ethylene pressure isincreased to 200 psig (1.48 MPa) and the quantity of 1-octene employedis 227 μL. Additional reagent amounts are listed in Table 6.

TABLE 6 Catalyst (C2) 250 μL  50 nmol Catalyst (C3) 300 μL  60 nmolCocatalyst 250 μL  60 nmol Cocatalyst 300 μL  72 nmol MMAO 250 μL  250nmol MMAO 300 μL  300 nmol PM 250 μL 2500 nmol PM 300 μL 3000 nmol

Conversion data collection is stopped after 10 minutes reaction or uponreaching a pressure drop to 120 psig (0.93 MPa). In order to betteraccount for the results obtained where reactions are terminated before10 minutes (because the target pressure is reached) the activity isevaluated based on the calculated 5 minute conversion, using thefollowing polymerization model:˜C*_(r)+M→˜C*_(r+1) k_(p) gaseous monomer propagation˜C*_(r)→DC k_(d) active site deactivationwhere:

˜C*_(r) is a growing chain with chain length r

M is the monomer

DC is dead polymer chain

k_(p) is the gaseous monomer propagation rate constant, and

k_(d) is the active site deactivation rate constant;

calculated as total gaseous monomer uptake versus time (t in seconds)according to the following equation:

$\begin{matrix}{{uptake} = \frac{k_{p} \cdot {{\lbrack M\rbrack_{liquid}\lbrack C\rbrack}_{0}\left\lbrack {1 - {\exp\left( {{- k_{d}} \cdot t} \right)}} \right\rbrack}}{k_{d}}} & {{Eq}\mspace{14mu} 1}\end{matrix}$

as determined according to the Levenberg-Marquart non-linear regressionmethod, where

[M]_(liquid) is the gaseous monomer concentration in the liquid phase,and

[C]₀ is the initial concentration of the catalyst at t=0.

Eq 1 is then used to fit the conversion-time data obtained from each PPRcell. A Levenberg-Marquart non-linear regression method, substantiallyas described in W.H. Press, S. A. Teukolsky, W. T. Vetterling, B. P.Flannery, “Numerical Recipes in C”, Second Edition, Cambridge UniversityPress (1997), is used to fit Eq 1 into the data and to estimate thekinetic rate constants k_(P) and k_(d). Then, by substituting theestimated rate constants for each cell into Eq 1, ethylene conversion(pressure drop in kPa) after 5 minutes (t=300 sec) is calculated andused to rank the catalyst activity in each PPR cell. The top tenrankings for both catalysts at 160° C. are shown in Table 7. The resultsare expressed relative to the average 5 minute monomer uptake obtainedusing no PM candidate (MMAO alone) at an Al:Ti molar ratio of 5:1 foreach metal complex. (The corresponding average 5 minute monomer uptakesusing MMAO are C2=541 kPa, C3=472 kPa.). Superscripts 1-10 indicateranking 1=best, 10=worst. All reported experiments had 5 minute monomeruptakes at least 42 percent greater than that obtained using MMAO alone(that is, relative activity=1.42).

TABLE 7 Ethylene/1-octene 160° C. Monomer Uptake Results (kPa)

Al(Et)₃ A2

1:1 2:1 1:1 2:1 1:1 2:1

C3 (1.63⁷) C2 (1.44⁹) C2 (1.53⁷) C3 (1.70⁷) C3 (1.51⁸)

C2 (1.52⁸) C3 (1.47⁹) C2 (1.58⁶) Ph—OH, C2 (1.65⁴) B10 C3 (1.69⁶)t-Bu—OH, C2 (1.70²) B11 C3 (1.80²)

1-dodecanol C2 (1.64⁵) B13 C3 (1.80³) 1-octadecanol B14 (t-Bu)(Me)₂SiOHC2 (1.82¹) C2 (1.42¹⁰) C2 (1.68³) B15 C3 (1.81¹) C3 (1.44¹⁰) C3 (1.69⁵)

By comparison of Tables 5 and 7 it is seen that the onlycatalyst/polymerization modifier combinations demonstrating improvementin activity at 135° C. and improvement in calculated 5 minute activityat 160° C. for both metal complexes are the 1:1 molar reaction productof (t-butyl)dimethylhydroxylsilane with tri(1-butyl)aluminum, that is,(t-butyldimethylsiloxy)di(isobutyl)aluminum and the 1:2 molar reactionproduct of (t-butyl)dimethylhydroxylsilane with trioctylaluminum, thatis, bis(t-butyldimethylsiloxy)octylaluminum.

Example 3

The reaction conditions of Example 2a) are substantially repeatedexcepting that the metal complex employed as a catalyst precursor is ans-indacenyl silanaminato complex of titanium,[N-(1,1-dimethylethyl)-1,1-dimethyl-[1,2,3,3a,8a-η)-1,5,6,7-tetrahydro-2-methyl-s-indacen-1-yl]silanaminto(2-)-N]titanium(II) 1,3-pentadiene (C4) (prepared according to the teachings of U.S.Pat. No. 5,965,756). The structure of C4 is disclosed in FIG. 4. Thecocatalyst is a mixture of methyldi(C₁₄₋₁₈) long chain alkyl ammoniumtetrakis(pentafluoro-phenyl)borate salts employed in a molar ratio basedon the catalyst precursor of 1.2:1. Triisobutyl-aluminum modifiedmethylalumoxane (MMAO-3A available from Akzo-Noble Corporation) (MMAO)is added as a scavenger in a molar ratio based on titanium of 5:1. Thepolymerization temperature is 135° C. All polymerizations are conductedin a mixed alkanes solvent (Isopar™ E, available from ExxonMobilChemicals, Inc.) at PM:Ti molar ratios of 50:1, 25:1 and 10:1. Theinitial ethylene pressure is 200 psig (1.48 MPa) and the quantity of1-octene employed is 227 μL. Controls are conducted in the absence of aPM candidate, all other reaction conditions remaining the same. PMcandidates demonstrating relative ethylene uptakes greater than 1.00after 10 minutes polymerization and the PM:Ti molar ratio (inparentheses) are contained in Table 8. All PM candidates listed are the1:1 molar reaction products of the identified reactants. Those compoundsdemonstrating improved activity are the reaction products ofphenylnaphthylamine, triethylhydroxysilane, n-butanol, or benzoic acidwith triisobutylaluminum; the reaction products of 2,6-diphenylphenol,4-methyl-2,6-di(t-butyl)phenol, triethylhydroxysilane, n-butanol or2-hydroxymethylfuran with trioctylaluminum; and the reaction products ofphenol or 2-(hydroxymethyl)pyridine with dibutylmagnesium. These metalcontaining compounds are identified as:(phenyl(naphthyl)amino)diisobutylaluminum,(triethylsiloxy)diisobutylaluminum, (n-butoxy)diisobutylaluminum,diisobutylaluminum benzoate; 2,6-diphenylphenoxy(dioctyl)aluminum,4-methyl-2,6-dit-butylphenoxy)dioctylaluminum,(triethylsiloxy)dioctylaluminum, (n-butoxy)dioctylaluminum,(2-furanylmethoxy)dioctylaluminum; phenoxy-n-butylmagnesium, and(2-pyridinylmethoxy)-n-butylmagnesium.

In addition, by using the foregoing multiple reactor an aluminumcompound lacking in Lewis base functionality was discovered to possessrelatively good activity under the present reaction conditions. Thecompound, di-1-butylaluminum hydride, possessed a relative activity of1.62 at a molar ratio based on Ti of 10:1.

The resulting LLDPE polymers are all higher density products than theproducts prepared in Example 2, and are suitable for use as film formingor blow molding resins.

TABLE 8 Ethylene/1-octene Copolymerization Relative Ethylene Uptake

(n-C₄H₉)₂Mg A6

— 1.93 (50) 1.92 (25) 1.92 (10) —

— 1.92 (50) 1.93 (10) 1.92 (25) — Ph—OH — — 1.63 (10) B10 1-dodecanol —— — B13 (t-Bu)(Me)₂SiOH — — — B15

1.92 (50) 1.92 (10) — —

— — 1.11 (10) (C₂H₅)₃SiOH 1.97 (50) 1.50 (50) — B26 1.55 (25) 2.02 (25)1.55 (10) 1.38 (10) n-C₄H₉OH 1.57 (50) 1.02 (50) — B27 1.82 (25)

— 1.84 (50) 1.72 (25) —

1.11 (50) 1.59 (25) 1.09 (10) — —

Example 4

The combinatorial reactors of Example 1 are employed to copolymerizeethylene and propylene (50:50 by weight) using a variety ofpolymerization modifiers. The metal complex employed as a catalystprecursor is2-[N-(2,6-diisopropylphenylamido)-o-isopropylphenylmethyl]-6-(2-η-1-naphthyl)-pyridylhafnium(IV) dimethyl (C5) (prepared according to the teachings of U.S.Ser. No. 60/429,024, filed May 2, 2003). The structure of C5 isdisclosed in FIG. 5. The cocatalyst used is a mixture ofmethyldi(C₁₄₋₁₈) long chain alkyl ammoniumtetrakis(pentafluorophenyl)borate salts employed in a molar ratio basedon hafnium of 1.2:1. Triisopropylaluminum modified methylalumoxane(MMAO-IP, available from Akzo-Noble Corporation) is added as a scavengerin a molar ratio based on hafnium of 30:1. Mixed alkanes solvent andscavenger followed by polymerization modifier (50:1, based on moles ofhafnium) and cocatalyst are added to each cell. The quantity of solventemployed (approximately 2 ml) is precalculated to provide a finalreaction mixture volume of 6.0 ml. The reactor is heated to the reactiontemperature of 120° C. with stirring and pressurized (250 psig, 1.83MPa) with the ethylene/propylene mixture before addition of the metalcomplex.

Polymerizations are conducted for 10 minutes or until a decrease ofpressure equal to maximum conversion of 120 percent. A total of 162polymerization modifiers are screened based on relative monomer uptakecompared to use of MMAO-IP alone (molar ratio to Hf=30:1). Selectedresults are presented in Table 9. Only 4 PM candidates (indicated inbold type) demonstrate relative monomer uptakes greater than 1. Onlythree PM candidates showed at least 10 percent improvement (relativemonomer uptake>1.1).

TABLE 9 Ethylene/Propylene Copolymerization Relative Monomer Uptake

Al(Et)₃ A2

1:1 2:1 1:1 2:1 1:1 2:1

0.63 0.82 0.22 0.16 1.07 0.90 (Me₃Si)₂NH 0.98 0.86 0.78 0.65 1.15 0.42B9 Ph—OH, 0.99 0.10 0.09 0.04 1.13 0.09 B10 1-dodecanol 0.08 0.07 0.060.07 1.17 0.08 B13 (t-Bu)(Me)₂SiOH 0.95 0.96 0.98 0.84 1.00 0.91 B15

0.09 0.09 0.05 0.03 0.98 0.05

By comparison of the results of Tables 8 and 9, it may be seen thatpolymerization modifiers having suitable properties for somepolymerizations, such as ethylene/1-octene copolymerizations are notnecessarily suited for use as polymerization modifiers in otherreactions, such as ethylene/propylene copolymerizations. Undercombinatorial screening conditions, only the 1:1 reaction products oftrioctylaluminum with 1-dodecanol, bis(trimethylsilyl)amine, phenol, and4-methyl-2,6-di(t-butyl)phenol showed improved ethylene relativeincorporation rates with the hafnium pyridyl amine metal complex,specifically2-[N-(2,6-diisopropylphenylamido)-o-isopropylphenylmethyl]-6-(2-η-1-naphthyl)-pyridylhafnium(IV) dimethyl and ammonium borate activator, specifically amixture of methyldi(C₁₄₋₁₈) long chain alkyl ammoniumtetrakis(pentafluorophenyl)borate salts with an alumoxane scavenger,specifically tri(isopropyl)aluminum modified methylalumoxane. Thesepolymerization modifiers are identified as (dodecyloxy)dioctylaluminum,(bis(trimethylsilyl)-amino)dioctylaluminum, phenoxydioctylaluminum, and(4-methyl-2,6-di-t-butylphenoxy)dioctyl-aluminum.

When the polymerization conditions of Example 4 are scaled up to a oneliter batch reactor under equivalent polymerization conditions, theforegoing PM candidates show superior performance under actual useconditions, illustrating the reliability of the foregoing screeningtechnique for predicting successful polymerization modifier performance.Other suitable polymerization modifiers under larger scale batchpolymerization conditions include (t-butyldimethylsiloxy)dioctylaluminumhaving a relative activity of 1.0 under combinatorial conditions (B15A5in Table 9), (bis(trimethylsilyl)amino)diethylaluminum, having arelative activity under combinatorial conditions of 0.78 (B9A2 in Table9), and bis(t-butyldimethylsiloxy)isopropylaluminum, having a relativeactivity under combinatorial conditions of 0.96 (B15₂A1 in Table 9).

1. A composition comprising a polymerization modifier for thecopolymerization of ethylene and propylene comprising(dodecyloxy)dioctylaluminum, (bis(trimethylsilyl)amino)dioctylaluminum,phenoxydioctylaluminum,(4-methyl-2,6-di(t-butyl)phenoxy)dioctylaluminum,(t-butyldimethylsiloxy) dioctylaluminum,bis(trimethylsilyl)aminodiethylaluminum, or bis(t-butyldimethylsiloxy)isopropylaluminum.
 2. The composition of claim 1 further comprising atransition metal complex and a cocatalyst.
 3. The composition of claim 2wherein the metal complex comprises a complex of hafnium and apyridylamine; and, the cocatalyst comprises tris(pentafluorophenyl)boronor a trialkylammonium salt of tetrakis(pentafluorophenyl)borate.
 4. Apolymerization process comprising contacting ethylene and propyleneunder polymerization conditions with the composition of claim
 2. 5. Thepolymerization process of claim 4 wherein the metal complex comprises acomplex of hafnium and a pyridylamine; and, the cocatalyst comprisestris(pentafluorophenyl)boron or a trialkylammonium salt oftetrakis(pentafluorophenyl)borate.
 6. The polymerization process ofclaim 4 wherein the metal complex comprises2[N-(2,6-diisopropylphenylamido)-o-isopropylphenylmethyl]-6-(2-η-1-naphthyl)-pyridylhafnium(IV) dimethyl, the cocatalyst comprises a mixture of methyldi(C₁₄₋₁₈) long chain alkyl ammonium tetrakis(pentafluorophenyl)borate salts.